Manganese and lithium-containing molecular precursors for battery cathode materials

ABSTRACT

Lithium-manganese-containing molecular precursor compounds, compositions and processes for making cathodes for lithium ion batteries. The molecular precursor compounds are soluble and provide processes to make cathode materials with controlled stoichiometry in a solution-based processes. The cathode material can be, for example, a lithium manganese oxide, a lithium manganese phosphate, or a lithium manganese silicate. Cathodes can be made as bulk material in a solid form or in solution, or in various forms including thin films.

BACKGROUND

The choice of cathode for a battery is significant in terms of thedesired performance and cost. The cathode composition is an importantfactor for the energy density that can be achieved. For lithium-ionbatteries, the choice of cathode can also involve a balance betweenpower available and energy utilization. Thus, the choice of cathode isimportant for the planned mode of application of the battery.

Useful candidates for cathode materials for lithium-ion batteriesinclude lithium metal oxides, lithium metal phosphates, and lithiummetal silicates.

A drawback in the field of lithium-ion batteries is the difficulty ofsynthesizing cathode material at moderate temperatures. Use of moderatetemperatures is desirable for production efficiency, but has been adrawback because it limits the choice of cathode material that can besynthesized via conventional processes. Conventional methods may requiretemperatures as high as 1000° C.

It is also desirable to provide cathode materials with a high degree ofcompositional homogeneity and control, as well as uniformity and purity.

Another problem is to provide cathode material having long termstability under various battery operating conditions.

A further drawback is that the properties desired for the battery, suchas energy density, lifecycle, and stability can require cathodematerials of high compositional uniformity.

These requirements can place a high value and strict conditions onprocesses for synthesizing cathode materials.

In addition to bulk materials for cathodes, various architectures formaking a lithium ion battery may require thin film cathodes. Forexample, a cathode can be formed as a thin film in a pattern to beinterspersed or interleaved with electrolyte and anode components. Thecathode itself can be composed of multiple thin film layers. Thedifficulties with these approaches include controlling the uniformity,purity and homogeneity of the cathode layers, as well as controllingcathode surface and edge quality.

Difficulties in the production of thin film cathodes include limitedability to deposit uniform layers of cathode material with sufficientspeed and throughput for commercial processes.

There has long been a continuing need for processes for synthesizingcathode materials for lithium ion batteries at moderate temperatures toprovide materials having a high degree of compositional homogeneity,uniformity and purity.

There is also a need for processes for making cathode materials thatprovide control over the composition and stoichiometry of the materials.

What is needed are soluble precursor compounds and compositions forprocesses for synthesizing cathode materials for lithium ion batteries.

BRIEF SUMMARY

This invention provides a range of molecular precursor compounds,compositions and processes used to prepare cathode materials for lithiumion battery devices.

This invention relates to molecular precursor compounds, compositionsand processes used to prepare cathode materials for lithium ion batterydevices. In particular, this invention relates to molecular precursorcompounds, compositions and processes for making bulk cathode materials,and cathodes in various forms including thin films.

Embodiments of this disclosure include:

A molecular precursor compound having the empirical formula [LiM(OR)₃],wherein M is Co, Mn or Ni, each of the —OR groups is independentlyselected from alkoxy, aryloxy, heteroaryloxy, alkenyloxy, siloxy,phosphinate, phosphonate, and phosphate.

A molecular precursor compound having the empirical formula [LiM(OR)₄],wherein M is Co, Mn or Ni, the —OR groups are independently, for eachoccurrence, selected from alkoxy, aryloxy, heteroaryloxy, alkenyloxy,siloxy, phosphinate, phosphonate, and phosphate.

The molecular precursor compound above, further comprising a number n ofcoordinating species L, having the empirical formula [LiM(OR)₄].n L,wherein n is from 0.1 to 8, and wherein L is selected from acetates,ethyl acetate, propyl acetates, n-propyl acetate, isopropyl acetate,butyl acetates, n-butyl acetate, sec-butyl acetate, isobutyl acetate,t-butyl acetate, isopentyl acetate, 2-methylbutyl acetate, 3-methylbutylacetate, 2,2-dimethylbutyl acetate, 2,3-dimethylbutyl acetate,2-methylpentyl acetate, 3-methylpentyl acetate, 4-methylpentyl acetate,2-methylhexyl acetate, 3-methylhexyl acetate, 4-methylhexyl acetate,5-methylhexyl acetate, 2,3-dimethylbutyl acetate, 2,3-dimethylpentylacetate, 2,4-dimethylpentyl acetate, 2,2-dimethylhexyl acetate,2,3-dimethylhexyl acetate, 2,4-dimethylhexyl acetate, 2,5-dimethylhexylacetate, 2,2-dimethylpentyl acetate, 3,3-dimethylpentyl acetate,3,3-dimethylhexyl acetate, 4,4-dimethylhexyl acetate, 2-ethylpentylacetate, 3-ethylpentyl acetate, 2-ethylhexyl acetate, 3-ethylhexylacetate, 4-ethylhexyl acetate, 2-methyl-2-ethylpentyl acetate,2-methyl-3-ethylpentyl acetate, 2-methyl-4-ethylpentyl acetate,2-methyl-2-ethylhexyl acetate, 2-methyl-3-ethylhexyl acetate,2-methyl-4-ethylhexyl acetate, 2,2-diethylpentyl acetate,3,3-diethylhexyl acetate, 2,2-diethylhexyl acetate, 3,3-diethylhexylacetate, n-heptyl acetate, n-octyl acetate, n-nonyl acetate, n-decylacetate, n-undecyl acetate, n-dodecyl acetate, n-tridecyl acetate,n-tetradecyl acetate, n-pentadecyl acetate, n-hexadecyl acetate,n-heptadecyl acetate, n-octadecyl acetate, esters, alkylesters,arylesters, ketones, alkylketones, arylketones, acetone, alcohols,diols, thiols, methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol,2-methylpropan-1-ol, butan-2-ol, 2-methylpropan-2-ol, pentanol, hexanol,ethers, alkylethers, arylethers, diethylether, tetrahydrofuran,2-methyl-tetrahydrofuran, amines, diamines, triamines, trimethylamine,ethylenediamine, acetonitrile, pyridine, and mixtures of the foregoing.

The molecular precursor compound above,

wherein the alkoxy groups are selected from methoxy, ethoxy, n-propoxy,1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy,3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy,2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy,1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy,2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy,1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxyor 1-ethyl-2-methylpropoxy, heptyloxy, octyloxy, 2-ethylhexyloxy,nonyloxy, decyloxy, aminoalkoxy —ORNR₂ where R is alkyl, alkoxyalkoxy—OROR where R is alkyl, phosphatoalkoxy —ORPR₂ where R is alkyl, andpositional isomers and combinations thereof;

wherein the dialkoxy groups are —OR²O— groups, wherein R² may be asubstituted or unsubstituted, branched or unbranched alkylene chain—(CH₂)_(q)—, where q is from 1 to 20;

wherein the siloxy groups are selected from OSi(OR¹)₃, —OSi(OR¹)₂R²,OSi(OR¹)R² ₂, and —OSiR² ₃, wherein R¹ and R² are independently, foreach occurrence, selected from alkyl, aryl, heteroaryl, alkenyl, silyl,and positional isomers and combinations thereof; and

wherein the phosphate groups are —OP(O)(OR¹)₂, the phosphonate groupsare —OP(O)(OR¹)R², and the phosphinate groups are —OP(O)R² ₂, wherein R¹and R² are independently, for each occurrence, selected from alkyl,aryl, heteroaryl, alkenyl, and silyl.

A molecular precursor compound having the empirical formulaLi₂M^(x+)(OR)_(2+x), wherein M is selected from Co, Mn and Ni, x isselected from 2 and 3, and the —OR groups are independently selectedfrom alkoxy, aryloxy, heteroaryloxy, alkenyloxy, siloxy, phosphinate,phosphonate, and phosphate.

A process for making a cathode material, the process comprising:providing one or more molecular precursor compounds above, or a mixturethereof; and heating the mixture at a temperature of from 100° C. to800° C. to convert it to a material.

A process for making a thin film cathode, the process comprising:providing a substrate coated with a current collector layer; providingan ink comprising one or more molecular precursor compounds above; anddepositing the ink onto the current collector layer; heating thedeposited ink at a temperature of from 100° C. to 800° C. to convert itto a material.

The process above, wherein the heating is performed with exposure to airor oxidizing atmosphere. The process above, wherein the heating isperformed under inert atmosphere after exposure to air or oxidizingatmosphere. The process above, further comprising annealing the materialat a temperature of from 400° C. to 800° C.

The process above, wherein the ink contains one or more dopant sourcecompounds having the formula M(OR)_(q), where M is selected from Mg, Y,Ti, Zr, Nb, Cr, Ru, B, Al, Bi, Sb, Sn, La, q is the same as theoxidation state of the atom M, and (OR) is independently selected fromalkoxy, aryloxy, heteroaryloxy, alkenyloxy, siloxy, phosphinate,phosphonate, and phosphate.

A cathode made by the process above. A lithium ion battery made with thecathode above.

A process for making an ink, the process comprising: providing amolecular precursor compound above; and dissolving the molecularprecursor compound in an acetate-solvent mixture comprising an acetateink component; wherein the acetate ink component is selected from alkylacetates, ethyl acetate, propyl acetates, butyl acetates, n-butylacetate, sec-butyl acetate, tert-butyl acetate, hexyl acetates, arylacetates, alkenyl acetates, and heteroaryl acetates; and wherein thesolvent is selected from alcohol, methanol, ethanol, isopropyl alcohol,sec-butanol, thiols, butanol, butanediol, glycerols, alkoxyalcohols,glycols, 1-methoxy-2-propanol, acetone, ethylene glycol, propyleneglycol, propylene glycol laurate, ethylene glycol ethers, diethyleneglycol, triethylene glycol monobutylether, propylene glycolmonomethylether, 1,2-hexanediol, ethers, diethyl ether, aliphatichydrocarbons, aromatic hydrocarbons, dodecane, hexadecane, pentane,hexane, heptane, octane, isooctane, decane, cyclohexane, p-xylene,m-xylene, o-xylene, benzene, toluene, xylene, tetrahydrofuran,2-methyltetrahydrofuran, siloxanes, cyclosiloxanes, silicone fluids,halogenated hydrocarbons, dibromomethane, dichloromethane,dichloroethane, trichloroethane chloroform, methylene chloride,acetonitrile, esters, acrylates, isobornyl acrylate, 1,6-hexanedioldiacrylate, polyethylene glycol diacrylate, ketones, methyl ethylketone, cyclohexanone, butyl carbitol, cyclopentanone, lactams,N-methylpyrrolidone, N-(2-hydroxyethyl)-pyrrolidone, cyclic acetals,cyclic ketals, aldehydes, amines, diamines, amides, dimethylformamide,methyl lactate, oils, natural oils, terpenes, and mixtures thereof.

A process for making a precursor compound, the process comprisingreacting M(NR¹ ₂)₂ or M(NR¹ ₂)₃ with R²OH and LiOR² in a solvent;

wherein M is Co, Mn or Ni;

wherein R¹ is alkyl, aryl, heteroaryl, or alkenyl, and the —OR² groupsare independently selected, for each occurrence, from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate; and

wherein the R²OH is selected from ethanol, isopropanol, sec-butanol,n-butanol, t-butanol, HOSi(OR³)₃, HOSi(OR³)₂R⁴, HOSi(OR³)R⁴ ₂, HOSiR⁴ ₃,and a diol HOR²OH, wherein R³ and R⁴ are independently selected fromalkyl, aryl, heteroaryl, or alkenyl.

A process for making a precursor compound, the process comprisingreacting M(NR¹ ₂)₂ or M(NR¹ ₂)₃ with R²OH and LiNR¹ ₂ in a solvent;

wherein M is Co, Mn or Ni;

wherein R¹ is alkyl, aryl, heteroaryl, or alkenyl, and the —OR² groupsare independently selected, for each occurrence, from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate; and

wherein R¹ is Si(CH₃)₃ and R²OH is selected from ethanol, isopropanol,sec-butanol, n-butanol, t-butanol, HOSi(OR³)₃, HOSi(OR³)₂R⁴, HOSi(OR³)R⁴₂, HOSiR⁴ ₃, and a diol HOR²OH, wherein R³ and R⁴ are independentlyselected from alkyl, aryl, heteroaryl, and alkenyl.

A process for making a precursor compound, the process comprisingreacting M(OR)₂ or M(OR)₃ with LiOR in a solvent, wherein M is Co, Mn orNi; wherein the —OR groups are independently selected, for eachoccurrence, from alkoxy, aryloxy, heteroaryloxy, alkenyloxy, siloxy,phosphinate, phosphonate, and phosphate.

A cathode material having the formula Li_((1+x))CoO_((2+x/2)), where xis from 0.01 to 1. The cathode material, wherein x is from 0.01 to 1, orfrom 0.01 to 0.5, or from 0.01 to 0.3, or from 0.01 to 0.2, or from 0.01to 0.1, or from 0.01 to 0.05. A cathode material having the formulaLi_((1+x))MnO_((2+x/2)), where x is from 0.01 to 1. The cathodematerial, wherein x is from 0.01 to 1, or from 0.01 to 0.5, or from 0.01to 0.3, or from 0.01 to 0.2, or from 0.01 to 0.1, or from 0.01 to 0.05.

A cathode material having the formula Li_((1+x))Co(PO_((4+x/2))), wherex is from 0.01 to 1. The cathode material, wherein x is from 0.01 to 1,or from 0.01 to 0.5, or from 0.01 to 0.3, or from 0.01 to 0.2, or from0.01 to 0.1, or from 0.01 to 0.05.

A cathode material having the formula Li_((1+x))Mn(PO_((4+x/2))), wherex is from 0.01 to 1. The cathode material, wherein x is from 0.01 to 1,or from 0.01 to 0.5, or from 0.01 to 0.3, or from 0.01 to 0.2, or from0.01 to 0.1, or from 0.01 to 0.05.

A cathode material having the formula Li_((1+x))NiO_((2+x/2)), where xis from 0.01 to 1. The cathode material, wherein x is from 0.01 to 1, orfrom 0.01 to 0.5, or from 0.01 to 0.3, or from 0.01 to 0.2, or from 0.01to 0.1, or from 0.01 to 0.05.

A cathode material having the formula Li_((1+x))Ni(PO_((4+x/2))), wherex is from 0.01 to 1. The cathode material, wherein x is from 0.01 to 1,or from 0.01 to 0.5, or from 0.01 to 0.3, or from 0.01 to 0.2, or from0.01 to 0.1, or from 0.01 to 0.05.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: FIG. 1 shows the empirical formulas forlithium-manganese-containing molecular precursor compoundsLiM^(x+)(OR)_(1+x) and Li₂M^(x+)(OR)_(2+x). The molecular precursorcompounds are used for making lithium ion battery cathode materials.

FIG. 2: FIG. 2 shows the X-ray diffraction pattern of a bulk LiCoO₂cathode material prepared from the cathode molecular precursor compoundLiCo(O^(s)Bu)₃ that was converted to a material and annealed in a tubefurnace at 650° C.

FIG. 3: FIG. 3 shows the Raman scattering spectrum for a thin film ofLiCoO₂ cathode prepared by inkjet printing of the molecular precursorcompound LiCo(O^(s)Bu)₃. The Raman spectrum shows the presence of thehigh temperature layered LiCoO₂ crystalline phase (˜485 cm⁻¹ and ˜595cm⁻¹).

FIG. 4: FIG. 4 shows the Raman scattering spectrum for a thin film ofLiCoO₂ cathode prepared by inkjet printing of the molecular precursorcompound LiCo(O^(s)Bu)₃. The Raman spectrum shows the presence of thehigh temperature layered LiCoO₂ crystalline phase (˜485 cm⁻¹ and ˜595cm⁻¹).

FIG. 5: FIG. 5 shows the results of ICP elemental analysis of differentbatches of LiCoO₂ Molecular Precursor Inks for use in forming LiCoO₂cathode films.

FIG. 6: FIG. 6 shows the ICP elemental analysis of LiCoO₂ MolecularPrecursor Inks and corresponding thin films of LiCoO₂ formed with theinks.

FIG. 7: Schematic representation of embodiments of this invention inwhich one or more molecular precursor compounds are designed andsynthesized for use in making cathode materials. FIG. 7 shows that thesoluble molecular precursor compounds can be used to form a solution.The molecular precursor compounds in the solution can be converted intoa material. The material in the solution can be used as a slurry, or thematerial can be isolated from the mixture. A final cathode material maybe made by annealing. The final cathode material is used in a lithiumion battery.

FIG. 8: Schematic representation of embodiments of this invention inwhich one or more molecular precursor compounds are designed andsynthesized for use in making cathode materials. FIG. 8 shows that themolecular precursor compounds can be used in solid form. The molecularprecursor compounds can be converted into a material. The material canbe transformed into a final cathode material by annealing. The finalcathode material is used in a lithium ion battery.

FIG. 9: Schematic representation of embodiments of this invention inwhich one or more molecular precursor compounds are designed andsynthesized for cathodes. FIG. 9 shows that the molecular precursorcompounds can be used to form an ink composition. The ink compositioncan be deposited onto a substrate by printing or spraying, and themolecular precursor compounds transformed into a cathode material. Thefinal cathode material is used in a lithium ion battery.

FIG. 10: Schematic representation of embodiments of this invention inwhich one or more molecular precursor compounds are prepared in-situ inan ink composition for making cathodes. The ink composition can bedeposited onto a substrate by printing or spraying, and optionally driedin a drying stage to form a molecular precursor film. The molecularprecursor compounds in the film may be converted and annealed to acathode material. The final cathode material is used in a lithium ionbattery.

FIG. 11: Schematic representation of a lithium ion battery embodiment ofthis invention.

DETAILED DESCRIPTION

This disclosure provides compounds, compositions and processes formaking cathode materials. In one aspect, this disclosure providesprocesses to make cathode materials using soluble molecular precursorcompounds. The molecular precursor compounds can be converted to highquality cathode materials. Thus, this invention provides molecularprecursor compounds that can be used for facile synthesis of cathodematerials.

Molecular precursor compounds of this disclosure have been designed andsynthesized for efficient processes to make cathodes. A molecularprecursor compound of this disclosure may be soluble in a solvent orsolvent mixture, or in a solvent containing an acetate component, or inan organic solvent.

The molecular precursor compounds of this disclosure are soluble incertain solvents and provide new ways to make cathode materials withtunable and controlled stoichiometry with solution-based processes. Thefinal cathodes can be, for example, a lithium cobalt oxide, a lithiumcobalt phosphate, a lithium cobalt silicate, a lithium manganese oxide,a lithium manganese phosphate, a lithium manganese silicate, a lithiumnickel oxide, a lithium nickel phosphate, or a lithium nickel silicate.

Molecular precursor compounds and compositions of this invention canadvantageously be used to make homogeneous cathode materials at moderatetemperatures, and for synthesis of cathode materials with controlledstoichiometry.

The molecular precursor compounds of this invention can be used to makebulk material for cathodes in different formats for various batteryapplications.

The molecular precursor compounds of this invention can also be used tomake cathodes as thin films. Thin films can be made by depositingmolecular precursor compounds onto a substrate and transforming thedeposited layer into a cathode material.

This invention provides a range of transition metal-containing molecularprecursor compounds to be used for making cathodes for lithium ionbatteries.

For example, FIG. 1 shows the empirical formulas forlithium-manganese-containing molecular precursor compoundsLiM^(x+)(OR)_(1+x) and Li₂M^(x+)(OR)_(2+x). The molecular precursorcompounds are used for making lithium ion battery cathode materials.

FIG. 2 shows the X-ray diffraction pattern of a bulk material LiCoO₂prepared from the cathode molecular precursor compound LiCo(O^(s)Bu)₃that was converted to a material and annealed in a tube furnace at 650°C.

FIG. 3 shows the Raman scattering spectrum for a thin film of LiCoO₂cathode prepared by inkjet printing of the molecular precursor compoundLiCo(O^(s)Bu)₃. The Raman spectrum shows the presence of the hightemperature layered LiCoO₂ crystalline phase (˜485 cm⁻¹ and ˜595 cm⁻¹).

FIG. 4 shows the Raman scattering spectrum for a thin film of LiCoO₂cathode prepared by inkjet printing of the molecular precursor compoundLiCo(O^(s)Bu)₃. The Raman spectrum shows the presence of the hightemperature layered LiCoO₂ crystalline phase (˜485 cm⁻¹ and ˜595 cm⁻¹).

Synthesis of Bulk Cathode Materials

Lithium ion batteries can be made using bulk cathode materials.

This disclosure provides a range of isolated molecular precursorcompounds which can be used in solid form, or can be solubilized forpreparing cathode materials. The isolated molecular precursor compoundsof this invention can overcome the drawbacks of attempting to usecathode compounds themselves for making cathodes.

The isolated molecular precursor compounds of this invention can haveunexpectedly advantageous solubility and properties for making cathodematerials.

The isolated molecular precursor compounds of this invention canadvantageously allow control of the stoichiometry of lithium andtransition metal atoms.

Cathodes Prepared from Solids:

In some aspects, this invention provides processes for making bulkcathode materials by converting a solid form of a molecular precursorcompound into a bulk material. The molecular precursor compound can beused as a neat solid to be converted to a cathode material.

Cathodes Prepared from Solutions:

In certain aspects, this invention provides processes for making cathodematerials by dissolving a molecular precursor compound in a solvent toform a solution, and converting the dissolved molecular precursorcompound into a bulk material. The solution of the molecular precursorcompound may contain a catalyst such as a Lewis acid catalyst orBronsted acid catalyst.

In some embodiments, the final liquor containing the bulk material thatwas produced can be used as a slurry to prepare a cathode coating foruse in battery production. In certain embodiments, the bulk material canbe isolated from the final liquor for additional processing.

The step of converting a molecular precursor compound into a cathodematerial, whether performed with neat solids or in solution, can be doneby thermal treatment. In some embodiments, a molecular precursorcompound can be converted into a material by the application of heat,light, kinetic, mechanical or other energy, or for example, UV light ormicrowave irradiation.

Embodiments of this invention advantageously provide processes formaking cathode materials at moderate temperatures.

The step of converting a molecular precursor compound into a materialcan be performed at a temperature of about 300° C. to about 500° C.

The step of converting a molecular precursor compound into a materialcan be performed at various temperatures including from about 100° C. toabout 800° C., or from about 150° C. to about 800° C., or from about200° C. to about 800° C., or from about 300° C. to about 800° C., orfrom about 400° C. to about 800° C., or from about 400° C. to about 700°C., or from about 400° C. to about 600° C., or from about 450° C. toabout 650° C., or from about 450° C. to about 600° C., or from about550° C. to about 650° C.

In some embodiments, a step of converting a molecular precursor compoundinto a material, whether performed with neat solids or in solution, canbe done with exposure to ambient air, or dry air, or air with controlledhumidity.

In some embodiments, a step of converting a molecular precursor compoundinto a material, whether performed with neat solids or in solution, canbe done in an inert atmosphere.

In certain embodiments, a step of converting a molecular precursorcompound into a material, whether performed with neat solids or insolution, can be done in an inert atmosphere after exposure of themolecular precursor compound to ambient air, or dry air, or air withcontrolled humidity.

In certain aspects, a step of converting a molecular precursor compoundinto a material, whether performed with neat solids or in solution, canbe done under oxidizing conditions or with exposure to an oxidizingatmosphere. Examples of an oxidizing atmosphere include 1% O₂/99% N₂,10% O₂/90% N₂, and air.

In certain aspects, a step of converting a mixture of molecularprecursor compounds into a material, whether performed with neat solidsor in solution, can be done under reducing conditions. Examples of areducing atmosphere include 1% H₂/99% N₂, and 5% H₂/95% N₂.

Processes for Final Cathode Materials

In further aspects, processes for making a cathode for a lithium ionbattery can include a step of converting a molecular precursor compound,or composition thereof, into a material or pre-cathode material,followed by a step of transforming the material into a final productcathode material.

A step of converting a material or pre-cathode material into a finalcathode material can be performed by thermal treatment.

In some embodiments, a cathode material or pre-cathode material can betransformed into a final cathode material by annealing.

A step of annealing a cathode material or pre-cathode material can beperformed under oxidizing conditions.

A step of annealing a cathode material or pre-cathode material can beperformed under dry air.

An annealing process may include a step of heating a material at atemperature sufficient to transform the material into a final cathodematerial, which may include growth of crystalline grains.

An annealing process may include a step of heating at a temperature offrom 400° C. to 800° C. for a time period of from 1 min to 60 min. Insome embodiments, an annealing process includes a step of heating asubstrate at a temperature of 400° C., or 450° C., or 500° C., or 600°C., or 650° C.

An annealing process may include a step of rapid thermal processing. Insome embodiments, rapid thermal processing may be performed by heatingat a rate from 1°/s to 100°/s.

Cathodes as Thin Films

In some aspects, one or more molecular precursor compounds of thisdisclosure may be combined to provide an ink composition. The propertiesof an ink composition may be controlled through the nature of themolecular precursor compounds and the ink components.

In certain aspects, a cathode may be fabricated by first depositing oneor more layers of a molecular precursor ink. An ink composition of thisinvention can achieve high throughput for deposition by printing orspraying processes.

Cathodes Prepared with Ink Compositions:

A cathode may be prepared in various embodiments by converting themolecular precursor compounds in a deposited ink into a cathode orpre-cathode material. The cathode or pre-cathode material may befinished by further annealing. In some embodiments, the cathode orpre-cathode material may be finished by depositing additional layers ofink and converting the molecular precursor compounds therein to amaterial.

In some embodiments, a step of converting a molecular precursor compoundinto a thin film material can be done with exposure to ambient air, ordry air, or air with controlled humidity.

In some embodiments, a step of converting a molecular precursor compoundinto a thin film material can be done in an inert atmosphere.

In certain embodiments, a step of converting a molecular precursorcompound into a thin film material can be done in an inert atmosphereafter exposure of the molecular precursor compound to ambient air, ordry air, or air with controlled humidity.

In certain aspects, a step of converting a molecular precursor compoundinto a thin film material can be done under oxidizing conditions or withexposure to an oxidizing atmosphere.

Molecular precursor compounds in various layers of ink deposited on asubstrate can be converted to a cathode composition by applying energyto the layered substrate. In some embodiments, one or more molecularprecursor compounds in a layer may be converted to a material before thedeposition of a succeeding layer. In certain embodiments, one or moremolecular precursor compounds in a group of layers can be converted atthe same time.

Molecular precursor compounds in a layer may be converted to a materialbefore, during or after the deposition of a different layer.

In further aspects, a lithium ion battery can be fabricated bydepositing solid layers of a cathode, an electrolyte composition, and ananode. Each of the cathode and anode can have an associated currentcollector to provide electrical current output. The electrolytecomposition or electrolyte portion of the battery may include aseparator to isolate anode from cathode while allowing lithium iontransport to and from both the anode and cathode.

One way to produce lithium ion batteries involves depositing solidlayers of a cathode, an electrolyte composition, and an anode, amongother things. The layers can be deposited in two or three dimensions. Alithium ion battery can be composed of a solid cathode layer and a solidanode layer separated by a layer of an electrolyte composition thatallows lithium ion transport to and from the anode and cathode.

Cathode layers could be made by printing, spraying, coating or othermethods involving solutions or inks. Aspects of this invention canprovide compounds and compositions to provide continuous transport of asolution or ink through an outlet, slot, die or print head. For example,inkjet printing can be performed with high throughput. Printing methodscan be enhanced by using molecular precursor compounds of this inventionthat are soluble components of the ink.

Aspects of this invention may provide processes for depositing cathodesby printing, spraying, coating, inkjet or other methods involvingsolutions or inks of molecular precursor compounds. An ink can bedeposited containing soluble cathode precursor compounds which can betransformed into a cathode material.

In general, this invention can provide stable ink forms which lackparticulates and are suitable for efficient printing, spraying, orcoating to make cathode materials.

Molecular Precursor Inks

Embodiments of this disclosure provide inks and ink compositionscontaining one or more molecular precursors.

In some aspects, inks and ink compositions may be made by dissolving orsolubilizing molecular precursor molecules in one or more organicsolvents.

In some embodiments, an ink for making cathode materials requires firstproviding one or more isolated molecular precursor compounds. Theisolated molecular precursor compounds may be used to prepare an inkcomposition that can be efficiently printed or deposited on a substrate.

This disclosure provides a range of isolated molecular precursorcompounds which can be solubilized for preparing an ink composition. Theisolated molecular precursor compounds of this invention providesuperior control of the lithium to transitional metal stoichiometry andcan overcome the drawbacks of attempting to use cathode compoundsthemselves for making thin film cathodes.

For example, FIG. 5 shows the results of ICP elemental analysis ofdifferent batches of LiCoO₂ Molecular Precursor Inks for use in formingLiCoO₂ cathode films.

FIG. 6 shows the ICP elemental analysis of LiCoO₂ Molecular PrecursorInks and corresponding thin films of LiCoO₂ formed with the inks.

The isolated molecular precursor compounds of this invention can haveunexpectedly advantageous solubility and properties for making an inkcomposition to be printed or deposited on a substrate.

The isolated molecular precursor compounds of this invention canadvantageously allow control of the stoichiometry of metal atoms in anink composition to be printed or deposited on a substrate.

In further aspects, inks and ink compositions may be made by directlysynthesizing molecular precursor molecules in an ink composition.

In some embodiments, one or more molecular precursor compounds formaking cathode materials can be prepared in-situ in an ink composition.The ink composition can be efficiently printed or deposited on asubstrate.

Ink compositions having one or more molecular precursor compoundsprepared in-situ during the ink forming process can advantageouslyprovide a stable ink for efficient trouble-free use in printing,spraying, coating and other methods.

Ink compositions having one or more molecular precursor compoundsprepared in-situ during the ink forming process can advantageouslyprovide a stable ink for use in printing, spraying, coating and othermethods.

Ink compositions of this invention having one or more molecularprecursor compounds prepared in-situ during the ink forming process canadvantageously allow control of the stoichiometry of lithium andtransition metal atoms in an ink composition to be printed or depositedon a substrate.

Processes for Depositing Molecular Precursors

The depositing of inks and molecular precursors can be done by printing,spraying, coating, and other methods.

As shown in FIG. 7, in certain embodiments, one or more molecularprecursor compounds 100 can be dissolved in solution 110. The solidmolecular precursor compounds may be converted 115 to form a cathodematerial, where the original liquor contains the formed cathodematerial. The liquor containing the formed cathode material can be usedas a slurry form 120 to make a cathode, or the cathode material can beisolated 120 for further processing into a cathode material 150. Alithium ion battery 160 can be fabricated with the cathode material.

As shown in FIG. 8, in certain embodiments, one or more molecularprecursor compounds 100 can be utilized in solid form 110. The solidmolecular precursor compounds may be converted 115 and/or annealed toform a cathode material 150. A lithium ion battery 160 can be fabricatedwith the cathode material.

As shown in FIG. 9, in certain embodiments, one or more molecularprecursor compounds 100 can be solubilized in an ink composition 110 anddeposited as an image 120 on a substrate. The molecular precursorcompounds may be converted and/or annealed to form a cathode material150. A lithium ion battery 160 can be fabricated with the cathodematerial.

As shown in FIG. 10, in certain embodiments, one or more molecularprecursor compounds 100 can be prepared and solubilized in-situ to forman ink composition 110. The ink composition 110 can be deposited as animage 120 on a substrate and optionally dried in a drying stage. Themolecular precursor compounds can be transformed into a molecular film130. The molecular precursor compounds can be further converted to forma pre-cathode material 140. The pre-cathode material 140 can be annealedto form a cathode material 150. Optionally, the molecular film 130 canbe annealed to directly form a cathode material. A lithium ion battery160 can be fabricated with the cathode material.

Each step of converting can optionally be done with exposure to ambientair, or dry air, or air with controlled humidity.

Each step of converting can be done in an inert atmosphere.

Each step of converting can also be done in an inert atmosphere afterexposure to ambient air, or dry air, or air with controlled humidity.

Each step of converting can optionally be done under oxidizingconditions or with exposure to an oxidizing atmosphere.

A patterned layer or image on a substrate can be composed of multiplelayers and/or images of an ink. In some embodiments, an image or layermay be converted to a pre-cathode material or cathode material before,during or after the depositing or printing of an additional image orlayer.

As used herein, converting refers to a process, for example a heating orthermal process, which converts one or more molecular precursorcompounds, which may be a solid, or contained in a solution, an ink orink composition, into a material. For example, the material may be apre-cathode material or a cathode material.

As used herein, annealing refers to a process, for example a heating orthermal process, which transforms a material from one form into anotherform. For example, a pre-cathode material can be annealed to provide acathode material.

As used herein, a component can be a compound, an element, a material,or a composition.

Isolated Molecular Precursor Compounds for Cathodes

This invention provides a range of cobalt, manganese andnickel-containing molecular precursor compounds for making cathodes forlithium ion batteries.

A structural feature of the molecular precursor compounds of thisinvention is that they contain lithium atoms along with cobalt,manganese or nickel atoms bound in the same precursor molecule. Ingeneral, the single molecular precursor molecule has, within itscompositional structure, both lithium atoms and transition metal atoms.Without wishing to be bound by any particular theory, the presence ofboth lithium atoms and transition metal atoms in the same precursormolecule provides pre-existing lithium-oxygen-metal atom linkages tofacilitate production of cathode materials.

The transitional metal-containing molecular precursor compounds of thisinvention can be used to make bulk material for cathodes, or thin filmcathodes.

The cathode molecular precursor compounds of this disclosure canadvantageously be used to control the lithium to cobalt, lithium tomanganese, and lithium to nickel stoichiometry.

The molecular precursors of this invention can have superiorprocessability to deposit thin films for making cathodes, and provideefficient processes for making cathodes.

In general, the structure and properties of the molecular precursorcompounds, inks, compositions, and materials of this invention provideadvantages in making cathodes, lithium ion batteries, and devicesregardless of the morphology, architecture, or manner of fabrication ofthe devices.

In general, a cathode molecular precursor compound may be a neutralcompound, or an ionic form, or have a charged complex or counterion.

In some embodiments, a cathode molecular precursor compound can berepresented in general as LiM^(x+)(OR)_(1+x), which is a compoundcontaining lithium, a transition metal having an oxidation state of x,and —OR groups. When the transition metal is Co, Mn or Ni, the oxidationstate x can be independently 2 or 3. The —OR groups can beindependently, for each occurrence, selected from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate.

In some embodiments, a cathode molecular precursor compound can berepresented in general as [LiM^(x+)(OR)_(1+x)].n L, where the compoundincludes a number n of coordinating species L.

In some embodiments, a cathode molecular precursor compound can berepresented in general as Li₂M^(x+)(OR)_(2+x), which is a compoundcontaining two lithium atoms, a transition metal having an oxidationstate x, and —OR groups. When the transition metal is Co, Mn or Ni theoxidation state x can be independently 2 or 3. The —OR groups can beindependently, for each occurrence, selected from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate.

In some embodiments, a cathode molecular precursor compound can berepresented in general as [Li₂M^(x+)(OR)_(2+x)].n L, where the compoundincludes a number n of coordinating species L.

Control of Lithium to Metal Stoichiometry in Cathodes with MolecularPrecursor Compounds

The molecular precursors of this invention can advantageously be used tocontrol the stoichiometry of lithium to metal in cathode materials.

In some embodiments, a mixture of molecular precursor compounds can beused to control the ratio of lithium to metal atoms. A mixture ofmolecular precursor compounds having the formulas LiM^(x+)(OR)_(1+x) andLi₂M^(y+)(OR)_(2+y) may be used, where x and y are the same or differentand are independently selected from 2 and 3, and where M is Co, Mn orNi, and the (OR) groups are as defined below.

In some aspects, a mixture of molecular precursor compounds can be usedgiven by Formula I

r.LiM^(x+)(OR)_(1+x)+s.Li₂M^(x+)(OR)_(2+x)=Li_((1+s))M(OR)_((1+s+x))  Formula I

where r+s=1, and x is the same in both compounds and is selected from 2and 3.

In certain embodiments, when x is 2, a mixture of molecular precursorcompounds having the formulas LiM(OR)₃ and Li₂M(OR)₄ may be used.

In certain embodiments, when x is 3, a mixture of molecular precursorcompounds having the formulas LiM(OR)₄ and Li₂M(OR)₅ may be used.

In some aspects, a mixture of molecular precursor compounds havingdifferent oxidation states of transitional metal atoms can be used. Forexample, a mixture of molecular precursor compounds having the formulasLiM(III)(OR)₄ and Li₂M(II)(OR)₄ may be used. In another example, amixture of molecular precursor compounds having the formulasLiM(II)(OR)₃ and Li₂M(III)(OR)₅ may be used.

In some embodiments, a mixture of molecular precursor compounds may havethe composition represented by the formula Li_((1+s))M(OR)_((3+s)),wherein the oxidation state of the metal atom M is x=2, s is from 0.01to 1, and the —OR groups are defined as above. The additional lithiumrepresented by s can be from s=0.01 to 1, or from 0.01 to 0.9, or from0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01 to0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2, orfrom 0.01 to 0.1, or from 0.01 to 0.05. In some embodiments, s is 0.01,or 0.05, or 0.1, or 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 0.8,or 0.9.

In some embodiments, a mixture of molecular precursor compounds may havethe composition represented by the formula Li_((1+s))M(OR)_((4+s)),wherein the oxidation state of the metal atom M is x=3, s is from 0.01to 1, and the —OR groups are defined as above. The additional lithiumrepresented by s can be from s=0.01 to 1, or from 0.01 to 0.9, or from0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01 to0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2, orfrom 0.01 to 0.1, or from 0.01 to 0.05. In some embodiments, s is 0.01,or 0.05, or 0.1, or 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 0.8,or 0.9.

In certain aspects, a mixture of molecular precursor compounds can beused to make a cathode material having the empirical formulaLi_((1+g))MO_((2+g/2)), where g is from 0 to 1.

In certain aspects, a mixture of molecular precursor compounds can beused to make a cathode material having the empirical formulaLi_((2+g))M(PO_((4+g/2))), where g is from 0 to 1.

In certain aspects, a mixture of molecular precursor compounds can beused to make a cathode material having the empirical formulaLi_((2+g))M(SiO_((4+g/2))), where g is from 0 to 1.

Structures of Isolated Molecular Precursor Compounds for Cathodes

In the formulas above, the —OR groups can be independently selected, foreach occurrence, from alkoxy, aryloxy, heteroaryloxy, alkenyloxy,siloxy, phosphinate, phosphonate, and phosphate.

In some embodiments, in the formulas above, the —OR groups can beindependently selected, for each occurrence, from alkoxy groups—OR^(alk) wherein R^(ack) can be independently selected, for eachoccurrence, from C(1-22)alkyl groups. In certain embodiments, R^(alk)can be independently selected, for each occurrence, from C(1-6)alkylgroups. In further embodiments, R^(alk) can be independently selected,for each occurrence, from ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl, t-butyl, isopentyl, 2-methylbutyl, 3-methylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl,and 4-methylpentyl.

In some embodiments, in the formulas above, the —OR groups can beindependently selected, for each occurrence, from aryloxy groups—OR^(aryl), wherein R^(aryl) can be independently selected, for eachoccurrence, from phenyl, alkyl substituted phenyl, naphthyl,tetrahydro-naphthyl, indanyl, and biphenyl.

In certain embodiments, in the formulas above, the —OR groups can beindependently selected, for each occurrence, from siloxy groupsOSi(OR^(sil))₃, —OSi(OR^(sil))₂R², OSi(OR^(sil))R² ₂, and —OSiR² ₃,wherein R^(sil) and R² can be independently selected, for eachoccurrence, from alkyl, aryl, heteroaryl, alkenyl, and silyl groups.

In certain embodiments, in the formulas above, the —OR groups can beindependently selected, for each occurrence, from alkoxysiloxy groups,alkoxyalkylsiloxy groups, and alkylsiloxy groups.

In the formulas above, the —OR groups can be independently selected, foreach occurrence, from phosphate groups —OP(O)(OR^(phos))₂, phosphonategroups —OP(O)(OR^(phos))R², and phosphinate groups —OP(O)R² ₂, whereinR^(phos) and R² can be independently selected, for each occurrence, fromalkyl, aryl, heteroaryl, alkenyl, and silyl groups.

Any of a phosphate group, a phosphonate group, and a phosphinate groupcan be terminal or bridging.

In some embodiments, a molecular precursor compound may have one or more—OR or —ORO— groups that are μ-2 or μ-3 bridging.

For example, the empirical formula LiM(OR)₃ can represent a moleculehaving one or more —OR or —ORO— groups that are μ-2 or μ-3 bridging.

In certain embodiments, a molecular precursor compound may have one ormore —OR(O)— groups that are carboxylate groups.

In certain embodiments, a molecular precursor compound may have one ormore —ORO— groups that are dialkoxy groups.

In some aspects, in the above formulas, the coordinating species L canbe molecules, functional groups, or moieties that interact with one ormore atoms of a molecular precursor compound.

In some aspects, in the above formulas, the coordinating species L canbe molecules of a coordinating solvent, coordinating molecular species,electron-donating groups, electron-donating species, or chelating groupsor species. Each of the n coordinating species L can be different fromthe others. A coordinating species L may be monodentate, bidentate ormultidentate. One or more of the coordinating species L in a formula maybe attached to a metal atom.

The number, n, of coordinating species L can be from zero to four, orfrom zero to eight.

The number, n, of coordinating species L can be from 0.1 to 0.5, or from0.1 to 1.0, or from 0.1 to 2, or from 0.1 to 3, or from 0.1 to 4.

The number, n, of coordinating species L can be 0.1, 0.2, 0.25, 0.3,0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 3.0, or 4.0.

Examples of Molecular Precursor Compounds

Preferred molecular precursor molecules of this invention may be basedon lithium-cobalt, lithium-manganese and lithium-nickel compounds.

In some embodiments, a cathode molecular precursor compound can berepresented by the empirical formula

[LiM(OR)^(d)(OR)^(e)(OR)^(f)]

where M is Co, Mn or Ni, and the —OR groups d, e and f are the same ordifferent and are as defined above.

In some embodiments, a cathode molecular precursor compound can berepresented by the empirical formula

[LiM(OR)^(d)(OR)^(e)(OR)^(f)(OR)^(g)]

where M is Co, Mn or Ni, and the —OR groups d, e, f and g are the sameor different and are as defined above.

In some embodiments, a cathode molecular precursor compound can berepresented by the empirical formula

[LiM(OR)^(d)(OR)^(e)(OR)^(f) ].n L

where M is Co, Mn or Ni, L is as defined below, and the —OR groups d, eand f are the same or different and are as defined above.

In some embodiments, a cathode molecular precursor compound can berepresented by the empirical formula

[LiM(OR)^(d)(OR)^(e)(OR)^(f)(OR)^(g) ].n L

where M is Co, Mn or Ni, L is as defined below, and the —OR groups d, e,f and g are the same or different and are as defined above.

In some embodiments, a cathode molecular precursor compound can berepresented by the empirical formula

[Li₂M(OR)^(d)(OR)^(e)(OR)^(f)(OR)^(g)]

where M is Co, Mn or Ni, and the —OR groups d, e, f and g are the sameor different and are as defined above.

In some embodiments, a cathode molecular precursor compound can berepresented by the empirical formula

[Li₂M(OR)^(d)(OR)^(e)(OR)^(f)(OR)^(g) ].n L

where M is Co, Mn or Ni, L is as defined below, and the —OR groups d, e,f and g are the same or different and are as defined above.

In some embodiments, a cathode molecular precursor compound can berepresented by the empirical formula

[Li₂m(OR)^(d)(OR)^(e)(OR)^(f)(OR)^(g)(OR)^(h)]

where M is Co, Mn or Ni, and the —OR groups d through h are the same ordifferent and are as defined above.

In some embodiments, a cathode molecular precursor compound can berepresented by the empirical formula

[Li₂M(OR)^(d)(OR)^(e)(OR)^(f)(OR)^(g)(OR)^(h) ].n L

where M is Co, Mn or Ni, L is as defined below, and the —OR groups dthrough h are the same or different and are as defined above.

Examples of molecular precursor compounds include [LiCo(O^(n)Bu)₃],[LiCo(O^(s)Bu)₃], [LiCo(O^(t)Bu)₃], [LiCo(O^(i)Pr)₃], [LiCo(O^(n)PR)₃],[LiCo(OEt)₃], [LiCo(O(n-pentyl))₃], [LiCo(O(n-hexyl))₃],[LiCo(O^(t)Bu)(O^(n)Bu)₂], [LiCo(O^(s)Bu)(O^(n)Bu)₂],[LiCo(O^(i)Pr)(O^(n)Bu)₂], [LiCo(O^(n)Bu)(O^(t)Bu)₂],[LiCo(O^(n)Bu)(O^(s)Bu)₂], [LiCo(O^(n)Bu)(O^(i)Pr)₂],[LiCo(O^(s)Bu)(O^(t)Bu)₂], [LiCo(O^(t)Bu)(O^(s)Bu)₂], and[LiCo(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)].

Examples of molecular precursor compounds include[LiCo(OP(O)(O^(n)Bu)₂)₃], [LiCo(OP(O)(O^(s)Bu)₂)₃],[LiCo(OP(O)(O^(t)Bu)₂)₃], [LiCo(OP(O)(O^(i)Pr)₂)₃],[LiCo(OP(O)(O^(n)Pr)₂)₃], [LiCo(OP(O)(OEt)₂)₃],[LiCo(OP(O)(O(n-pentyl))₂)₃], [LiCo(OP(O)(O(n-hexyl))₂)₃],[LiCo(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂], [LiCo(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₂],[LiCo(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₂], [LiCo(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₂],[LiCo(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₂], [LiCo(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₂],[LiCo(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₂], [LiCo(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₂],and [LiCo(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)].

Examples of molecular precursor compounds include[LiCo(OSi(O^(t)Bu)₃)₃], [LiCo(OSi(O^(t)Bu)₂ ^(s)Bu)₃],[LiCo(OSi(O^(t)Bu)^(s)Bu₂)₃], [LiCo(OSi^(s)Bu₃)₃],[LiCo(O^(n)Bu)(OSi(O^(t)Bu)₃)₂], and [LiCo(O^(n)Bu)(OSi(O^(t)Bu)₂^(n)Bu)₂].

Examples of molecular precursor compounds include [LiCo(O^(n)Bu)₄],[LiCo(O^(s)Bu)₄], [LiCo(O^(t)Bu)₄], [LiCo(O^(i)Pr)₄], [LiCo(O^(n)Pr)₄],[LiCo(OEt)₄], [LiCo(O(n-pentyl))₄], [LiCo(O(n-hexyl))₄],[LiCo(O^(t)Bu)(O^(n)Bu)₃], [LiCo(O^(s)Bu)(O^(n)Bu)₃],[LiCo(O^(i)Pr)(O^(n)Bu)₃], [LiCo(O^(n)Bu)(O^(t)Bu)₃],[LiCo(O^(n)Bu)(O^(s)Bu)₃], [LiCo(O^(n)Bu)(O^(i)Pr)₃],[LiCo(O^(s)Bu)(O^(t)Bu)₃], [LiCo(O^(t)Bu)(O^(s)Bu)₃], and[LiCo(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].

Examples of molecular precursor compounds include[LiCo(OP(O)(O^(n)Bu)₂)₄], [LiCo(OP(O)(O^(s)Bu)₂)₄],[LiCo(OP(O)(O^(t)Bu)₂)₄], [LiCo(OP(O)(O^(i)Pr)₂)₄],[LiCo(OP(O)(O^(n)Pr)₂)₄], [LiCo(OP(O)(OEt)₂)₄],[LiCo(OP(O)(O(n-pentyl))₂)₄], [LiCo(OP(O)(On-hexyl)₂)₄],[LiCo(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃], [LiCo(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃],[LiCo(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃], [LiCo(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃],[LiCo(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃], [LiCo(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃],[LiCo(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃], [LiCo(O^(t)Bu)(OP(O)(O^(s)Bu)₂)₃],and [LiCo(OP(O)(O^(n)Bu)₂)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].

Examples of molecular precursor compounds include[LiCo(OSi(O^(t)Bu)₃)₄], [LiCo(OSi(O^(t)Bu)₂ ^(s)Bu)₄],[LiCo(OSi(O^(t)Bu)^(s)Bu₂)₄], [LiCo(OSi^(s)Bu₃)₄],[LiCo(O^(n)Bu)₂(OSi(O^(t)Bu)₃)₂], and [LiCo(O^(n)Bu)₂(OSi(O^(t)Bu)₂^(n)Bu)₂].

Examples of molecular precursor compounds include [LiCo(O^(n)Bu)₃].n L,[LiCo(O^(s)Bu)₃].n L, [LiCo(O^(t)Bu)₃].n L, [LiCo(O^(i)Pr)₃].n L,[LiCo(O^(n)Pr)₃].n L, [LiCo(OEt)₃].n L, [LiCo(O(n-pentyl))₃].n L,[LiCo(O(n-hexyl))₃].n L, [LiCo(O^(t)Bu)(O^(n)Bu)₂].n L,[LiCo(O^(s)Bu)(O^(n)Bu)₂].n L, [LiCo(O^(i)Pr)(O^(n)Bu)₂].n L,[LiCo(O^(n)Bu)(O^(t)Bu)₂].n L, [LiCo(O^(n)Bu)(O^(s)Bu)₂].n L,[LiCo(O^(n)Bu)(O^(i)Pr)₂].n L, [LiCo(O^(s)Bu)(O^(t)Bu)₂].n L,[LiCo(O^(t)Bu)(O^(s)Bu)₂].n L, and [LiCo(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)].nL.

Examples of molecular precursor compounds include[LiCo(OP(O)(O^(n)Bu)₂)₃].n L, [LiCo(OP(O)(O^(s)Bu)₂)₃].n L,[LiCo(OP(O)(O^(t)Bu)₂)₃].n L, [LiCo(OP(O)(O^(i)Pr)₂)₃].n L,[LiCo(OP(O)(O^(n)Pr)₂)₃].n L, [LiCo(OP(O)(OEt)₂)₃].n L,[LiCo(OP(O)(O(n-pentyl))₂)₃].n L, [LiCo(OP(O)(O(n-hexyl))₂)₃].n L,[LiCo(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂].n L,[LiCo(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂].n L,[LiCo(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₂].n L,[LiCo(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₂].n L,[LiCo(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₂].n L,[LiCo(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₂].n L,[LiCo(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₂].n L,[LiCo(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₂].n L, and[LiCo(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)].n L.

Examples of molecular precursor compounds include[LiCo(OSi(O^(t)Bu)₃)₃].n L, [LiCo(OSi(O^(t)Bu)₂ ^(s)Bu)₃].n L,[LiCo(OSi(O^(t)Bu)^(s)Bu₂)₃].n L, [LiCo(OSi^(s)Bu₃)₃].n L,[LiCo(O^(n)Bu)(OSi(O^(t)Bu)₃)₂].n L, and [LiCo(O^(n)Bu)(OSi(O^(t)Bu)₂^(n)Bu)₂].n L.

Examples of molecular precursor compounds include [LiCo(O^(n)Bu)₄].n L,[LiCo(O^(s)Bu)₄].n L, [LiCo(O^(t)Bu)₄].n L, [LiCo(O^(i)Pr)₄].n L,[LiCo(O^(n)Pr)₄].n L, [LiCo(OEt)₄].n L, [LiCo(O(n-pentyl))₄].n L,[LiCo(O(n-hexyl))₄].n L, [LiCo(O^(t)Bu)(O^(n)Bu)₃].n L,[LiCo(O^(s)Bu)(O^(n)Bu)₃].n L, [LiCo(O^(i)Pr)(O^(n)Bu)₃].n L,[LiCo(O^(n)Bu)(O^(t)Bu)₃].n L, [LiCo(O^(n)Bu)(O^(s)Bu)₃].n L,[LiCo(O^(n)Bu)(O^(i)Pr)₃].n L, [LiCo(O^(s)Bu)(O^(t)Bu)₃].n L,[LiCo(O^(t)Bu)(O^(s)Bu)₃].n L, and[LiCo(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].n L.

Examples of molecular precursor compounds include[LiCo(OP(O)(O^(n)Bu)₂)₄].n L, [LiCo(OP(O)(O^(s)Bu)₂)₄].n L,[LiCo(OP(O)(O^(t)Bu)₂)₄].n L, [LiCo(OP(O)(O^(i)Pr)₂)₄].n L,[LiCo(OP(O)(O^(n)Pr)₂)₄].n L, [LiCo(OP(O)(OEt)₂)₄].n L,[LiCo(OP(O)(O(n-pentyl))₂)₄].n L, [LiCo(OP(O)(On-hexyl)₂)₄].n L,[LiCo(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃].n L,[LiCo(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃].n L,[LiCo(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃].n L,[LiCo(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃].n L,[LiCo(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃].n L,[LiCo(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃].n L,[LiCo(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃].n L,[LiCo(O^(t)Bu)(OP(O)(O^(s)Bu)₂)₃].n L, and[LiCo(OP(O)(O^(n)Bu)₂)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].n L.

Examples of molecular precursor compounds include[LiCo(OSi(O^(t)Bu)₃)₄].n L, [LiCo(OSi(O^(t)Bu)₂ ^(s)Bu)₄].n L,[LiCo(OSi(O^(t)Bu)^(s)Bu₂)₄].n L, [LiCo(OSi^(s)Bu₃)₄].n L,[LiCo(O^(n)Bu)₂(OSi(O^(t)Bu)₃)₂].n L, and [LiCo(O^(n)Bu)₂(OSi(O^(t)Bu)₂^(n)Bu)₂].n L.

Examples of molecular precursor compounds include [Li₂Co(O^(n)Bu)₄],[Li₂Co(O^(s)Bu)₄], [Li₂Co(O^(t)Bu)₄], [Li₂Co(O^(i)Pr)₄],[Li₂Co(O^(n)Pr)₄], [Li₂Co(OEt)₄], [Li₂Co(O(n-pentyl))₄],[Li₂Co(O(n-hexyl))₄], [Li₂Co(O^(t)Bu)(O^(n)Bu)₃],[Li₂Co(O^(t)Bu)(O^(n)Bu)₃], [Li₂Co(O^(i)Pr)(O^(n)Bu)₃],[Li₂Co(O^(n)Bu)(O^(t)Bu)₃], [Li₂Co(O^(n)Bu)(O^(s)Bu)₃],[Li₂Co(O^(n)Bu)(O^(i)Pr)₃], [Li₂Co(O^(s)Bu)(O^(t)Bu)₃],[Li₂Co(O^(t)Bu)(O^(s)Bu)₃], and [Li₂Co(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)₂].

Examples of molecular precursor compounds include[Li₂Co(OP(O)(O^(n)Bu)₂)₄], [Li₂Co(OP(O)(O^(s)Bu)₂)₄],[Li₂Co(OP(O)(O^(t)Bu)₂)₄], [Li₂Co(OP(O)(O^(i)Pr)₂)₄],[Li₂Co(OP(O)(O^(n)Pr)₂)₄], [Li₂Co(OP(O)(OEt)₂)₄],[Li₂Co(OP(O)(O(n-pentyl))₂)₄], [Li₂Co(OP(O)(O(n-hexyl))₂)₄],[Li₂Co(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃], [Li₂Co(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃],[Li₂Co(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃], [Li₂Co(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃],[Li₂Co(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃], [Li₂Co(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃],[Li₂Co(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃], [Li₂Co(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₃],and [Li₂Co(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)₂].

Examples of molecular precursor compounds include [Li₂Co(OSi(O^(t)Bu)₄],[Li₂Co(OSi(O^(t)Bu)₂ ^(s)Bu)₄], [Li₂Co(OSi(O^(t)Bu)^(s)Bu₂)₄],[Li₂Co(OSi^(s)Bu₃)₄], [Li₂Co(O^(n)Bu)(OSi(O^(t)Bu)₃)₃], and[Li₂Co(O^(n)Bu)(OSi(O^(t)Bu)₂ ^(n)Bu)₃].

Examples of molecular precursor compounds include [Li₂Co(O^(n)Bu)₅],[Li₂Co(O^(s)Bu)₅], [Li₂Co(O^(t)Bu)₅].

Examples of molecular precursor compounds include[Li₂Co(OP(O)(O^(n)Bu)₂)₅], [Li₂Co(OP(O)(O^(s)Bu)₂)₅],[Li₂Co(OP(O)(O^(t)Bu)₃)₅].

Examples of molecular precursor compounds include [Li₂Co(OSi(O^(t)Bu)₅],[Li₂Co(OSi(O^(t)Bu)₂ ^(s)Bu)₅], [Li₂Co(OSi(O^(t)Bu)^(s)Bu₂)₅],[Li₂Co(OSi^(s)Bu₃)₅], [Li₂Co(O^(n)Bu)₂(OSi(O^(t)Bu)₃)₃], and[Li₂Co(O^(n)Bu)₂(OSi(O^(t)Bu)₂ ^(n)Bu)₃]

Examples of molecular precursor compounds include [LiMn(O^(n)Bu)₃],[LiMn(O^(s)Bu)₃], [LiMn(O^(t)Bu)₃], [LiMn(O^(i)Pr)₃], [LiMn(O^(n)Pr)₃],[LiMn(OEt)₃], [LiMn(O(n-pentyl))₃], [LiMn(O(n-hexyl))₃],[LiMn(O^(t)Bu)(O^(n)Bu)₂], [LiMn(O^(s)Bu)(O^(n)Bu)₂],[LiMn(O^(i)Pr)(O^(n)Bu)₂], [LiMn(O^(n)Bu)(O^(t)Bu)₂],[LiMn(O^(n)Bu)(O^(s)Bu)₂], [LiMn(O^(n)Bu)(O^(i)Pr)₂],[LiMn(O^(s)Bu)(O^(t)Bu)₂], [LiMn(O^(t)Bu)(O^(s)Bu)₂], and[LiMn(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)].

Examples of molecular precursor compounds include[LiMn(OP(O)(O^(n)Bu)₂)₃], [LiMn(OP(O)(O^(s)Bu)₂)₃],[LiMn(OP(O)(O^(t)Bu)₂)₃], [LiMn(OP(O)(O^(i)Pr)₂)₃],[LiMn(OP(O)(O^(n)PO₂)₃], [LiMn(OP(O)(OEt)₂)₃],[LiMn(OP(O)(O(n-pentyl))₂)₃], [LiMn(OP(O)(O(n-hexyl))₂)₃],[LiMn(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂], [LiMn(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₂],[LiMn(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₂], [LiMn(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₂],[LiMn(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₂], [LiMn(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₂],[LiMn(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₂], [LiMn(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₂],and [LiMn(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)].

Examples of molecular precursor compounds include[LiMn(OSi(O^(t)Bu)₃)₃], [LiMn(OSi(O^(t)Bu)₂ ^(s)Bu)₃],[LiMn(OSi(O^(t)Bu)^(s)Bu₂)₃], [LiMn(OSi^(s)Bu₃)₃],[LiMn(O^(n)Bu)(OSi(O^(t)Bu)₃)₂], and [LiMn(O^(n)Bu)(OSi(O^(t)Bu)₂^(n)Bu)₂].

Examples of molecular precursor compounds include [LiMn(O^(n)Bu)₄],[LiMn(O^(s)Bu)₄], [LiMn(O^(t)Bu)₄], [LiMn(O^(i)Pr)₄], [LiMn(O^(n)Pr)₄],[LiMn(OEt)₄], [LiMn(O(n-pentyl))₄], [LiMn(O(n-hexyl))₄],[LiMn(O^(t)Bu)(O^(n)Bu)₃], [LiMn(O^(s)Bu)(O^(n)Bu)₃],[LiMn(O^(i)Pr)(O^(n)Bu)₃], [LiMn(O^(t)Bu)(O^(n)Bu)₃],[LiMn(O^(t)Bu)(O^(s)Bu)₃], [LiMn(O^(n)Bu)(O^(i)Pr)₃],[LiMn(O^(s)Bu)(O^(t)Bu)₃], [LiMn(O^(t)Bu)(O^(s)Bu)₃], and[LiMn(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].

Examples of molecular precursor compounds include[LiMn(OP(O)(O^(n)Bu)₂)₄], [LiMn(OP(O)(O^(s)Bu)₂)₄],[LiMn(OP(O)(O^(t)Bu)₂)₄], [LiMn(OP(O)(O^(i)Pr)₂)₄],[LiMn(OP(O)(O^(n)Pr)₂)₄], [LiMn(OP(O)(OEt)₂)₄],[LiMn(OP(O)(O(n-pentyl))₂)₄], [LiMn(OP(O)(On-hexyl)₂)₄],[LiMn(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃], [LiMn(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃],[LiMn(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃], [LiMn(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃],[LiMn(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃], [LiMn(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃],[LiMn(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃], [LiMn(O^(t)Bu)(OP(O)(O^(s)Bu)₂)₃],and [LiMn(OP(O)(O^(n)Bu)₂)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].

Examples of molecular precursor compounds include[LiMn(OSi(O^(t)Bu)₃)₄], [LiMn(OSi(O^(t)Bu)₂ ^(s)Bu)₄],[LiMn(OSi(O^(t)Bu)^(s)Bu₂)₄], [LiMn(OSi^(s)Bu₃)₄],[LiMn(O^(t)Bu)(OSi(O^(t)Bu)₃)₃], and [LiMn(O^(n)Bu)₂(OSi(O^(t)Bu)₂^(n)Bu)₂].

Examples of molecular precursor compounds include [Li₂Mn(O^(n)Bu)₄],[Li₂Mn(O^(s)Bu)₄], [Li₂Mn(O^(t)Bu)₄], [Li₂Mn(O^(i)Pr)₄],[Li₂Mn(O^(n)Pr)₄], [Li₂Mn(OEt)₄], [Li₂Mn(O(n-pentyl))₄],[Li₂Mn(O(n-hexyl))₄], [Li₂Mn(O^(t)Bu)(O^(n)Bu)₃],[Li₂Mn(O^(s)Bu)(O^(n)Bu)₃], [Li₂Mn(O^(i)Pr)(O^(n)Bu)₃],[Li₂Mn(O^(n)Bu)(O^(t)Bu)₃], [Li₂Mn(O^(n)Bu)(O^(s)Bu)₃],[Li₂Mn(O^(n)Bu)(O^(i)Pr)₃], [Li₂Mn(O^(s)Bu)(O^(t)Bu)₃],[Li₂Mn(O^(t)Bu)(O^(s)Bu)₃], and [Li₂Mn(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)₂].

Examples of molecular precursor compounds include[Li₂Mn(OP(O)(O^(n)Bu)₂)₄], [Li₂Mn(OP(O)(O^(s)Bu)₂)₄],[Li₂Mn(OP(O)(O^(t)Bu)₂)₄], [Li₂Mn(OP(O)(O^(i)Pr)₂)₄],[Li₂Mn(OP(O)(O^(n)Pr)₂)₄], [Li₂Mn(OP(O)(OEt)₂)₄],[Li₂Mn(OP(O)(O(n-pentyl))₂)₄], [Li₂Mn(OP(O)(O(n-hexyl))₂)₄],[Li₂Mn(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃], [Li₂Mn(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃],[Li₂Mn(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃], [Li₂Mn(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃],[Li₂Mn(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃], [Li₂Mn(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃],[Li₂Mn(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃], [Li₂Mn(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₃],and [Li₂Mn(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)₂].

Examples of molecular precursor compounds include[Li₂Mn(OSi(O^(t)Bu)₃)₄], [Li₂Mn(OSi(O^(t)Bu)₂ ^(s)Bu)₄],[Li₂Mn(OSi(O^(t)Bu)^(s)Bu₂)₄], [Li₂Mn(OSi^(s)Bu₃)₄],[Li₂Mn(O^(n)Bu)(OSi(O^(t)Bu)₃)₃], and [Li₂Mn(O^(n)Bu)(OSi(O^(t)Bu)₂^(n)Bu)₃].

Examples of molecular precursor compounds include [Li₂Mn(O^(n)Bu)₅],[Li₂Mn(O^(s)Bu)₅], [Li₂Mn(O^(t)Bu)₅].

Examples of molecular precursor compounds include[Li₂Mn(OP(O)(O^(n)Bu)₂)₅], [Li₂Mn(OP(O)(O^(s)Bu)₂)₅],[Li₂Mn(OP(O)(O^(t)Bu)₅].

Examples of molecular precursor compounds include[Li₂Mn(OSi(O^(t)Bu)₃)₅], [Li₂Mn(OSi(O^(t)Bu)₂ ^(s)Bu)₅],[Li₂Mn(OSi(O^(t)Bu)^(s)Bu₂)₅], [Li₂Mn(OSi^(s)Bu₃)₅],[Li₂Mn(O^(n)Bu)₂(OSi(O^(t)Bu)₃)₃], and [Li₂Mn(O^(n)Bu)₂(OSi(O^(t)Bu)₂^(n)Bu)₃].

Examples of molecular precursor compounds include [LiMn(O^(n)Bu)₃].n L,[LiMn(O^(s)Bu)₃].n L, [LiMn(O^(t)Bu)₃].n L, [LiMn(O^(i)Pr)₃].n L,[LiMn(O^(n)Pr)₃].n L, [LiMn(OEt)₃].n L, [LiMn(O(n-pentyl))₃].n L,[LiMn(O(n-hexyl))₃].n L, [LiMn(O^(t)Bu)(O^(n)Bu)₂].n L,[LiMn(O^(s)Bu)(O^(n)Bu)₂].n L, [LiMn(O^(i)Pr)(O^(n)Bu)₂].n L,[LiMn(O^(n)Bu)(O^(t)Bu)₂].n L, [LiMn(O^(n)Bu)(O^(s)Bu)₂].n L,[LiMn(O^(n)Bu)(O^(i)Pr)₂].n L, [LiMn(O^(s)Bu)(O^(t)Bu)₂].n L,[LiMn(O^(t)Bu)(O^(s)Bu)₂].n L, and [LiMn(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)].nL.

Examples of molecular precursor compounds include[LiMn(OSi(O^(t)Bu)₃)₃].n L, [LiMn(OSi(O^(t)Bu)₂ ^(s)Bu)₃].n L,[LiMn(OSi(O^(t)Bu)^(s)Bu₂)₃].n L, [LiMn(OSi^(s)Bu₃)₃].n L,[LiMn(O^(n)Bu)(OSi(O^(t)Bu)₃)₂].n L, and [LiMn(O^(n)Bu)(OSi(O^(t)Bu)₂^(n)Bu)₂].n L.

Examples of molecular precursor compounds include [LiMn(O^(n)Bu)₄].n L,[LiMn(O^(s)Bu)₄].n L, [LiMn(O^(t)Bu)₄].n L, [LiMn(O^(i)Pr)₄].n L,[LiMn(O^(n)Pr)₄].n L, [LiMn(OEt)₄].n L, [LiMn(O(n-pentyl))₄].n L,[LiMn(O(n-hexyl))₄].n L, [LiMn(O^(t)Bu)(O^(n)Bu)₃].n L,[LiMn(O^(s)Bu)(O^(n)Bu)₃].n L, [LiMn(O^(i)Pr)(O^(n)Bu)₃].n L,[LiMn(O^(n)Bu)(O^(t)Bu)₃].n L, [LiMn(O^(n)Bu)(O^(s)Bu)₃].n L,[LiMn(O^(n)Bu)(O^(i)Pr)₃].n L, [LiMn(O^(s)Bu)(O^(t)Bu)₃].n L,[LiMn(O^(t)Bu)(O^(s)Bu)₃].n L, and[LiMn(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].n L.

Examples of molecular precursor compounds include[LiMn(OP(O)(O^(n)Bu)₂)₃].n L, [LiMn(OP(O)(O^(s)Bu)₂)₃].n L,[LiMn(OP(O)(O^(t)Bu)₂)₃].n L, [LiMn(OP(O)(O^(i)Pr)₂)₃].n L,[LiMn(OP(O)(O^(n)Pr)₂)₃].n L, [LiMn(OP(O)(OEt)₂)₃].n L,[LiMn(OP(O)(O(n-pentyl))₂)₃].n L, [LiMn(OP(O)(O(n-hexyl))₂)₃].n L,[LiMn(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂].n L,[LiMn(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂].n L,[LiMn(O^(n)Pr)(OP(O)(O^(n)Bu)₂)₂].n L,[LiMn(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₂].n L,[LiMn(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₂].n L,[LiMn(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₂].n L,[LiMn(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₂].n L,[LiMn(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₂].n L, and[LiMn(OP(O)(O^(n)Pr)₂)(O^(t)Bu)(O^(s)Bu)].n L.

Examples of molecular precursor compounds include[LiMn(OP(O)(O^(n)Bu)₂)₄].n L, [LiMn(OP(O)(O^(s)Bu)₂)₄].n L,[LiMn(OP(O)(O^(t)Bu)₂)₄].n L, [LiMn(OP(O)(O^(i)Pr)₂)₄].n L,[LiMn(OP(O)(O^(n)Pr)₂)₄].n L, [LiMn(OP(O)(OEt)₂)₄].n L,[LiMn(OP(O)(O(n-pentyl))₂)₄].n L, [LiMn(OP(O)(On-hexyl)₂)₄].n L,[LiMn(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃].n L,[LiMn(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃].n L,[LiMn(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃].n L,[LiMn(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃].n L,[LiMn(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃].n L,[LiMn(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃].n L,[LiMn(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃].n L,[LiMn(O^(t)Bu)(OP(O)(O^(s)Bu)₂)₃].n L, and[LiMn(OP(O)(O^(n)Bu)₂)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].n L.

Examples of molecular precursor compounds include [LiNi(O^(n)Bu)₃],[LiNi(O^(s)Bu)₃], [LiNi(O^(t)Bu)₃], [LiNi(O^(i)Pr)₃], [LiNi(O^(n)Pr)₃],[LiNi(OEt)₃], [LiNi(O(n-pentyl))₃], [LiNi(O(n-hexyl))₃],[LiNi(O^(t)Bu)(O^(n)Bu)₂], [LiNi(O^(s)Bu)(O^(n)Bu)₂],[LiNi(O^(i)Pr)(O^(n)Bu)₂], [LiNi(O^(n)Bu)(O^(t)Bu)₂],[LiNi(O^(n)Bu)(O^(s)Bu)₂], [LiNi(O^(n)Bu)(O^(i)Pr)₂],[LiNi(O^(s)Bu)(O^(t)Bu)₂], [LiNi(O^(t)Bu)(O^(s)Bu)₂], and[LiNi(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)].

Examples of molecular precursor compounds include[LiNi(OP(O)(O^(n)Bu)₂)₃], [LiNi(OP(O)(O^(s)Bu)₂)₃],[LiNi(OP(O)(O^(t)Bu)₂)₃], [LiNi(OP(O)(O^(i)Pr)₂)₃],[LiNi(OP(O)(O^(n)Pr)₂)₃], [LiNi(OP(O)(OEt)₂)₃],[LiNi(OP(O)(O(n-pentyl))₂)₃], [LiNi(OP(O)(O(n-hexyl))₂)₃],[LiNi(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂], [LiNi(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₂],[LiNi(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₂], [LiNi(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₂],[LiNi(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₂], [LiNi(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₂],[LiNi(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₂], [LiNi(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₂],and [LiNi(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)].

Examples of molecular precursor compounds include[LiNi(OSi(O^(t)Bu)₃)₃], [LiNi(OSi(O^(t)Bu)₂ ^(s)Bu)₃],[LiNi(OSi(O^(t)Bu)^(s)Bu₂)₃], [LiNi(OSi^(s)Bu₃)₃],[LiNi(O^(n)Bu)(OSi(O^(t)Bu)₃)₂], and [LiNi(O^(n)Bu)(OSi(O^(t)Bu)₂^(n)Bu)_(z)].

Examples of molecular precursor compounds include [LiNi(O^(n)Bu)₄],[LiNi(O^(s)Bu)₄], [LiNi(O^(t)Bu)₄], [LiNi(O^(i)Pr)₄], [LiNi(O^(n)Pr)₄],[LiNi(OEt)₄], [LiNi(O(n-pentyl))₄], [LiNi(O(n-hexyl))₄],[LiNi(O^(t)Bu)(O^(n)Bu)₃], [LiNi(O^(s)Bu)(O^(n)Bu)₃],[LiNi(O^(i)Pr)(O^(n)Bu)₃], [LiNi(O^(n)Bu)(O^(t)Bu)₃],[LiNi(O^(n)Bu)(O^(s)Bu)₃], [LiNi(O^(n)Bu)(O^(i)Pr)₃],[LiNi(O^(s)Bu)(O^(t)Bu)₃], [LiNi(O^(t)Bu)(O^(s)Bu)₃], and[LiNi(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].

Examples of molecular precursor compounds include[LiNi(OP(O)(O^(n)Bu)₂)₄], [LiNi(OP(O)(O^(s)Bu)₂)₄],[LiNi(OP(O)(O^(t)Bu)₂)₄], [LiNi(OP(O)(O^(i)Pr)₂)₄],[LiNi(OP(O)(O^(n)Pr)₂)₄], [LiNi(OP(O)(OEt)₂)₄],[LiNi(OP(O)(O(n-pentyl))₂)₄], [LiNi(OP(O)(On-hexyl)₂)₄],[LiNi(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃], [LiNi(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃],[LiNi(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃], [LiNi(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃],[LiNi(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃], [LiNi(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃],[LiNi(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃], [LiNi(O^(t)Bu)(OP(O)(O^(s)Bu)₂)₃],and [LiNi(OP(O)(O^(n)Bu)₂)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].

Examples of molecular precursor compounds include[LiNi(OSi(O^(t)Bu)₃)₄], [LiNi(OSi(O^(t)Bu)₂ ^(s)Bu)₄],[LiNi(OSi(O^(t)Bu)^(s)Bu₂)₄], [LiNi(OSi^(s)Bu₃)₄],[LiNi(O^(n)Bu)(OSi(O^(t)Bu)₃)₃], and [LiNi(O^(n)Bu)₂(OSi(O^(t)Bu)₂^(n)Bu)₂].

Examples of molecular precursor compounds include [Li₂Ni(O^(n)Bu)₄],[Li₂Ni(O^(s)Bu)₄], [Li₂Ni(O^(t)Bu)₄], [Li₂Ni(O^(i)Pr)₄],[Li₂Ni(O^(n)Pr)₄], [Li₂Ni(OEt)₄], [Li₂Ni(O(n-pentyl))₄],[Li₂Ni(O(n-hexyl))₄], [Li₂Ni(O^(t)Bu)(O^(n)Bu)₃],[Li₂Ni(O^(s)Bu)(O^(n)Bu)₃], [Li₂Ni(O^(i)Pr)(O^(n)Bu)₃],[Li₂Ni(O^(n)Bu)(O^(t)Bu)₃], [Li₂Ni(O^(n)Bu)(O^(s)Bu)₃],[Li₂Ni(O^(n)Bu)(O^(i)Pr)₃], [Li₂Ni(O^(s)Bu)(O^(t)Bu)₃],[Li₂Ni(O^(t)Bu)(O^(s)Bu)₃], and [Li₂Ni(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)₂].

Examples of molecular precursor compounds include[Li₂Ni(OP(O)(O^(n)Bu)₂)₄], [Li₂Ni(OP(O)(O^(s)Bu)₂)₄],[Li₂Ni(OP(O)(O^(t)Bu)₂)₄], [Li₂Ni(OP(O)(O^(i)Pr)₂)₄],[Li₂Ni(OP(O)(O^(n)Pr)₂)₄], [Li₂Ni(OP(O)(OEt)₂)₄],[Li₂Ni(OP(O)(O(n-pentyl))₂)₄], [Li₂Ni(OP(O)(O(n-hexyl))₂)₄],[Li₂Ni(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃], [Li₂Ni(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃],[Li₂Ni(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃], [Li₂Ni(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃],[Li₂Ni(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃], [Li₂Ni(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃],[Li₂Ni(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃], [Li₂Ni(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₃],and [Li₂Ni(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)₂].

Examples of molecular precursor compounds include[Li₂Ni(OSi(O^(t)Bu)₃)₄], [Li₂Ni(OSi(O^(t)Bu)₂ ^(s)Bu₄],[Li₂Ni(OSi(O^(t)Bu)^(s)Bu₂)₄], [Li₂Ni(OSi^(s)Bu₃)₄],[Li₂Ni(O^(n)Bu)(OSi(O^(t)Bu)₃)₃], and [Li₂Ni(O^(n)Bu)(OSi(O^(t)Bu)₂^(n)Bu)₃].

Examples of molecular precursor compounds include [Li₂Ni(O^(n)Bu)₅],[Li₂Ni(O^(s)Bu)₅], [Li₂Ni(O^(t)Bu)₅].

Examples of molecular precursor compounds include[Li₂Ni(OP(O)(O^(n)Bu)₂)₅], [Li₂Ni(OP(O)(O^(s)Bu)₂)₅],[Li₂Ni(OP(O)(O^(t)Bu)₂)₅].

Examples of molecular precursor compounds include[Li₂Ni(OSi(O^(t)Bu)₃)₅], [Li₂Ni(OSi(O^(t)Bu)₂ ^(s)Bu)₅],[Li₂Ni(OSi(O^(t)Bu)^(s)Bu₂)₅], [Li₂Ni(OSi^(s)Bu₃)₅],[Li₂Ni(O^(n)Bu)₂(OSi(O^(t)Bu)₃)₃], and [Li₂Ni(O^(n)Bu)₂(OSi(O^(t)Bu)₂^(n)Bu)₃].

Examples of molecular precursor compounds include [LiNi(O^(n)Bu)₃].n L,[LiNi(O^(s)Bu)₃].n L, [LiNi(O^(t)Bu)₃].n L, [LiNi(O^(i)Pr)₃].n L,[LiNi(O^(n)Pr)₃].n L, [LiNi(OEt)₃].n L, [LiNi(O(n-pentyl))₃].n L,[LiNi(O(n-hexyl))₃].n L, [LiNi(O^(t)Bu)(O^(n)Bu)₂].n L,[LiNi(O^(s)Bu)(O^(n)Bu)₂].n L, [LiNi(O^(i)Pr)(O^(n)Bu)₂].n L,[LiNi(O^(n)Bu)(O^(t)Bu)₂].n L, [LiNi(O^(n)Bu)(O^(s)Bu)₂].n L,[LiNi(O^(n)Bu)(O^(i)Pr)₂].n L, [LiNi(O^(s)Bu)(O^(t)Bu)₂].n L,[LiNi(O^(t)Bu)(O^(s)Bu)₂].n L, and [LiNi(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)].nL.

Examples of molecular precursor compounds include[LiNi(OSi(O^(t)Bu)₃)₃].n L, [LiNi(OSi(O^(t)Bu)₂ ^(s)Bu)₃].n L,[LiNi(OSi(O^(t)Bu)^(s)Bu₂)₃].n L, [LiNi(OSi^(s)Bu₃)₃].n L,[LiNi(O^(n)Bu)(OSi(O^(t)Bu)₃)₂].n L, and [LiNi(O^(n)Bu)(OSi(O^(t)Bu)₂^(n)Bu)₂].n L.

Examples of molecular precursor compounds include [LiNi(O^(n)Bu)₄].n L,[LiNi(O^(s)Bu)₄].n L, [LiNi(O^(t)Bu)₄].n L, [LiNi(O^(i)Pr)₄].n L,[LiNi(O^(n)Pr)₄].n L, [LiNi(OEt)₄].n L, [LiNi(O(n-pentyl))₄].n L,[LiNi(O(n-hexyl))₄].n L, [LiNi(O^(t)Bu)(O^(n)Bu)₃].n L,[LiNi(O^(s)Bu)(O^(n)Bu)₃].n L, [LiNi(O^(i)Pr)(O^(n)Bu)₃].n L,[LiNi(O^(n)Bu)(O^(t)Bu)₃].n L, [LiNi(O^(n)Bu)(O^(s)Bu)₃].n L,[LiNi(O^(n)Bu)(O^(i)Pr)₃].n L, [LiNi(O^(s)Bu)(O^(t)Bu)₃].n L,[LiNi(O^(t)Bu)(O^(s)Bu)₃].n L, and[LiNi(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].n L.

Examples of molecular precursor compounds include[LiNi(OP(O)(O^(n)Bu)₂)₃].n L, [LiNi(OP(O)(O^(s)Bu)₂)₃].n L,[LiNi(OP(O)(O^(t)Bu)₂)₃].n L, [LiNi(OP(O)(O^(i)Pr)₂)₃].n L,[LiNi(OP(O)(O^(n)Pr)₂)₃].n L, [LiNi(OP(O)(OEt)₂)₃].n L,[LiNi(OP(O)(O(n-pentyl))₂)₃].n L, [LiNi(OP(O)(O(n-hexyl))₂)₃].n L,[LiNi(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂].n L,[LiNi(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂].n L,[LiNi(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₂].n L,[LiNi(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₂].n L,[LiNi(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₂].n L,[LiNi(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₂].n L,[LiNi(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₂].n L,[LiNi(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₂].n L, and[LiNi(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)].n L.

Examples of molecular precursor compounds include[LiNi(OP(O)(O^(n)Bu)₂)₄].n L, [LiNi(OP(O)(O^(s)Bu)₂)₄].n L,[LiNi(OP(O)(O^(t)Bu)₂)₄].n L, [LiNi(OP(O)(O^(i)Pr)₂)₄].n L,[LiNi(OP(O)(O^(n)Pr)₂)₄].n L, [LiNi(OP(O)(OEt)₂)₄].n L,[LiNi(OP(O)(O(n-pentyl))₂)₄].n L, [LiNi(OP(O)(On-hexyl)₂)₄].n L,[LiNi(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃].n L,[LiNi(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃].n L,[LiNi(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃].n L,[LiNi(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃].n L,[LiNi(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃].n L,[LiNi(O^(n)Bu)(OP(O)(O^(i)Pr)₂)₃].n L,[LiNi(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃].n L,[LiNi(O^(t)Bu)(OP(O)(O^(s)Bu)₂)₃].n L, and[LiNi(OP(O)(O^(n)Bu)₂)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].n L.

Any of the foregoing cathode molecular precursor compounds can be foundin a monomeric, dimeric, trimeric, or multimeric form.

Coordinating Species L

Examples of coordinating species L include acetates, ethyl acetate,propyl acetates, n-propyl acetate, isopropyl acetate, butyl acetates,n-butyl acetate, sec-butyl acetate, isobutyl acetate, t-butyl acetate,isopentyl acetate, 2-methylbutyl acetate, 3-methylbutyl acetate,2,2-dimethylbutyl acetate, 2,3-dimethylbutyl acetate, 2-methylpentylacetate, 3-methylpentyl acetate, 4-methylpentyl acetate, 2-methylhexylacetate, 3-methylhexyl acetate, 4-methylhexyl acetate, 5-methylhexylacetate, 2,3-dimethylbutyl acetate, 2,3-dimethylpentyl acetate,2,4-dimethylpentyl acetate, 2,2-dimethylhexyl acetate, 2,3-dimethylhexylacetate, 2,4-dimethylhexyl acetate, 2,5-dimethylhexyl acetate,2,2-dimethylpentyl acetate, 3,3-dimethylpentyl acetate,3,3-dimethylhexyl acetate, 4,4-dimethylhexyl acetate, 2-ethylpentylacetate, 3-ethylpentyl acetate, 2-ethylhexyl acetate, 3-ethylhexylacetate, 4-ethylhexyl acetate, 2-methyl-2-ethylpentyl acetate,2-methyl-3-ethylpentyl acetate, 2-methyl-4-ethylpentyl acetate,2-methyl-2-ethylhexyl acetate, 2-methyl-3-ethylhexyl acetate,2-methyl-4-ethylhexyl acetate, 2,2-diethylpentyl acetate,3,3-diethylhexyl acetate, 2,2-diethylhexyl acetate, 3,3-diethylhexylacetate, n-heptyl acetate, n-octyl acetate, n-nonyl acetate, n-decylacetate, n-undecyl acetate, n-dodecyl acetate, n-tridecyl acetate,n-tetradecyl acetate, n-pentadecyl acetate, n-hexadecyl acetate,n-heptadecyl acetate, n-octadecyl acetate, esters, alkylesters,arylesters, ketones, alkylketones, arylketones, acetone, alcohols,diols, thiols, methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol,2-methylpropan-1-ol, butan-2-ol, 2-methylpropan-2-ol, pentanol, hexanol,ethers, alkylethers, arylethers, diethylether, tetrahydrofuran,2-methyl-tetrahydrofuran, amines, diamines, triamines, trimethylamine,ethylenediamine, acetonitrile, pyridine, and mixtures of the foregoing.

Molecular Precursors

In solution, a molecular precursor of this invention having theempirical formula [Li₂M(OR)₄].n L may have structural Formula 2A

where L is as defined above and may be the same or different, and the—OR groups are as defined above.

In Formula 2A, the molecular precursor may have from one to eightcoordinating species L, and two coordinating species L may be attachedto each other when binding to the same metal atom.

In solution, a molecular precursor of this invention having theempirical formula [LiM(OR)₃].L₂ may have the structural Formula 2B

where L is as defined above and may be the same or different, and the—OR groups are as defined above.

In Formula 2B, the molecular precursor may have from one to eightcoordinating species L, and two coordinating species L may be attachedto each other when binding to the same metal atom. The dotted bonds inFormula 2A indicate that the coordinating species L are optionallypresent, and/or optionally attached to each other.

In certain embodiments, one or more of the coordinating species L may beattached to a metal atom M.

In solution, a molecular precursor of this invention having theempirical formula [LiM(OR)₃].n L may have the structural Formula 2C

where each M is Co, Mn or Ni, L is as defined above and may be the sameor different, and the —OR groups are as defined above.

In solution, a molecular precursor of this invention having theempirical formula [LiM(OR)₃].n L may have the structural Formula 2D

where each M is Co, Mn or Ni, L is as defined above and may be the sameor different, n is from ½ to eight, and the —OR groups are as definedabove.

In solution, a molecular precursor of this invention having theempirical formula [LiM(ORO)(OR)₂].n L may have the structural Formula 2E

where M is Co, Mn or Ni, L is as defined above, n is from ½ to eight,the —OR²O— groups are dialkoxy groups wherein R² may be a substituted orunsubstituted, branched or unbranched alkylene chain —(CH₂)_(q)—, whereq is from 1 to 20, and the —OR¹ are as defined above. In someembodiments, the —OR²O— groups can be bridging phosphonate, phosphinate,or phosphate groups, wherein —OR²O— represents —OP(O)(OR⁴)_(2-x)R⁵ _(x)—as shown below

where x is 0, 1 or 2, and groups R⁴ and R⁵ can be independently, foreach occurrence, alkyl, aryl, heteroaryl, alkenyl, silyl, and inorganicand organic groups.

In solution, a molecular precursor of this invention having theempirical formula [Li₂M₂(ORO)(OR)₄].n L may have the structural 2F

where M is Co, Mn or Ni, L is as defined above, n is from ½ to eight,the —OR¹O— groups are dialkoxy groups wherein R¹ may be a substituted orunsubstituted, branched or unbranched alkylene chain —(CH₂)_(q)—, whereq is from 1 to 20, and the —OR groups are as defined above.

In some embodiments, a molecular precursor compound may have one or more—OR or —ORO— groups that are μ-2 or μ-3 bridging.

For example, the empirical formula LiM(OR)₃ can represent a moleculehaving one or more —OR or —ORO— groups that are μ-2 or μ-3 bridging.

In certain embodiments, a molecular precursor compound may have one ormore —OR(O)— groups that are carboxylate groups.

In certain embodiments, a molecular precursor compound may have one ormore —ORO— groups that are dialkoxy groups.

In some embodiments, a molecular precursor compound may exist in adimeric form under ambient conditions, or a trimeric or higher form, andcan be used as a reagent in such forms. It is understood that the termcompound refers to all such forms, whether found under ambientconditions, or found during the process for synthesizing a molecularprecursor.

The molecular precursors of this invention can be advantageously solublein one or more organic solvents.

For the molecular precursors of this invention, the group R in theformulas above, or a portion thereof, may be a good leaving group inrelation to a transition of the molecular precursor compound at elevatedtemperatures or upon application of energy.

Examples of R alkyl groups include methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl,n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl,n-heptadecyl and n-octadecyl.

Examples of R alkyl groups include isopropyl, sec-butyl, isobutyl,tert-butyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylbutyl,2,3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl,2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl,2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl,2,5-dimethylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl,3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl,2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl,2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl,2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl,3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.

Examples of —OR alkoxy groups include alkoxyalkyl, alkoxyalkoxy, andalkylcarbonyl.

Examples of —OR alkoxy groups include methoxy, ethoxy, n-propoxy,1-methylethoxy(isopropoxy), butoxy, 1-methylpropoxy(sec-butoxy),2-methylpropoxy(isobutoxy) or 1,1-dimethylethoxy(tert-butoxy), pentoxy,1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy,1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy,1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy,1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy,2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy,1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy,1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or1-ethyl-2-methylpropoxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy,decyloxy, and positional isomers thereof.

Examples of R aryl groups include phenyl, naphthyl, anthracenyl, andphenanthrenyl.

In further embodiments, the groups R may independently be (C1-22)alkylgroups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl(propyl), or a(C4)alkyl(butyl), or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl, or a (C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a(C16)alkyl, or a (C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a(C20)alkyl, or a (C21)alkyl, or a (C22)alkyl.

In certain embodiments, the groups R may independently be (C1-12)alkylgroups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl.

In certain embodiments, the groups R may independently be (C1-6)alkylgroups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl.

A molecular precursor compound may be crystalline, or non-crystalline.

Preparation of Molecular Precursors

Embodiments of this invention provide a family of molecular precursormolecules and compositions.

Advantageously facile routes for the synthesis and isolation ofmolecular precursor compounds of this invention have been discovered, asdescribed below.

This disclosure provides a range of molecular precursor compositionswhich can be transformed into cathodes and cathode materials. In someaspects, the molecular precursor compositions are precursors for theformation of cathodes.

In some aspects, a molecular precursor compound can be made by ReactionScheme 1

where M is selected from Co, Mn and Ni, n is from 0 to 4, R¹ is alkyl,aryl, heteroaryl, alkenyl, or silyl, and the —OR² groups can beindependently selected, for each occurrence, from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate.

In Reaction Scheme 1, M(NR¹ ₂)₂ is reacted with an alcohol and LiOR² toprovide a molecular precursor.

In some embodiments, M(NR¹ ₂)₂ is reacted with an alcohol and a lithiumalkoxide to provide a molecular precursor.

In some embodiments, R²OH is HOSi(OR³)₃, HOSi(OR³)₂R⁴, HOSi(OR³)R⁴ ₂, orHOSiR⁴ ₃, wherein R³ and R⁴ are independently selected from alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, LiOR² is LiOSi(OR⁴)₃, wherein R⁴ is alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, R²OH is HOP(O)(OR⁵)₂, or HOP(O)(OR⁵)R⁵, or HOP(O)R⁵₂, wherein R⁵ is alkyl, aryl, heteroaryl, or alkenyl.

In some embodiments, LiOR² is LiOP(O)(OR⁶)₂, or LiOP(O)(OR⁶)R⁶, orLiOP(O)R⁶ ₂, wherein R⁶ is alkyl, aryl, heteroaryl, or alkenyl.

In some aspects, a molecular precursor compound can be made by ReactionScheme 2

where M is selected from Co, Mn and Ni, n is from 0 to 4, R¹ is alkyl,aryl, heteroaryl, alkenyl, or silyl; the —OR³ groups can beindependently selected, for each occurrence, from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate; and the R² of the —OR²O— groups can be alkylene,alkylene-aryl-alkylene, or alkylene-alkenyl-alkylene. Examples ofalkylene include —(CH₂)_(q)—, where q is from 1 to 20. An alkylene groupmay be branched or unbranched, or substituted or unsubstituted.

In Reaction Scheme 2, M(NR¹ ₂)₂ is reacted with a diol and LiOR³ toprovide a molecular precursor.

In some embodiments, M(NR¹ ₂)₂ is reacted with a diol and a lithiumalkoxide to provide a molecular precursor.

[Li(OR)M(ORO)] may from a dimer or multimer, [Li(OR)M(ORO)]_(x), where xis two or more.

In some embodiments, LiOR³ is LiOSi(OR⁴)₃, wherein R⁴ is alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, LiOR³ is LiOP(O)(OR⁵)₂, or LiOP(O)(OR⁵)R⁶, orLiOP(O)R⁶ ₂, wherein R⁶ is alkyl, aryl, heteroaryl, or alkenyl.

In some aspects, a molecular precursor compound can be made by ReactionScheme 3

where M is selected from Co, Mn and Ni, n is from 0 to 4, R¹ can beindependently selected, for each occurrence, from alkyl, aryl,heteroaryl, alkenyl, and silyl, and the OR² groups can be independentlyselected, for each occurrence, from alkoxy, aryloxy, heteroaryloxy,alkenyloxy, siloxy, phosphinate, phosphonate, and phosphate.

In Reaction Scheme 3, M(NR¹ ₂)₂ is reacted with an alcohol and LiNR¹ ₂to provide a molecular precursor.

In some embodiments, M(NR¹ ₂)₂ is reacted with an alcohol and a lithiumamine to provide a molecular precursor.

In some embodiments, R²OH is HOP(O)(OR⁵)₂, or HOP(O)(OR⁵)R⁶, or HOP(O)R⁵₂, wherein R⁵ is alkyl, aryl, heteroaryl, or alkenyl, and R⁶ is alkyl,aryl, heteroaryl, or alkenyl.

In some embodiments, molecular precursor compounds are made by followingreaction:

where R is ethyl, isopropyl, sec-butyl, n-butyl, or t-butyl.

In some aspects, a molecular precursor compound can be made by ReactionScheme 4

where M is selected from Co, Mn and Ni, n is from 0 to 8, R¹ can beindependently selected, for each occurrence, from alkyl, aryl,heteroaryl, alkenyl, and silyl, and the —OR² groups can be independentlyselected, for each occurrence, from alkoxy, aryloxy, heteroaryloxy,alkenyloxy, siloxy, phosphinate, phosphonate, and phosphate.

In Reaction Scheme 4, M(NR¹ ₂)₃ is reacted with an alcohol and LiOR² toprovide a molecular precursor.

In some embodiments, M(NR¹ ₂)₃ is reacted with an alcohol and a lithiumalkoxide to provide a molecular precursor.

In some embodiments, R²OH is HOSi(OR³)₃, HOSi(OR³)₂R⁴, HOSi(OR³)R⁴ ₂, orHOSiR⁴ ₃, wherein R³ and R⁴ are independently selected from alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, LiOR² is LiOSi(OR⁴)₃, wherein R⁴ is alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, R²OH is HOP(O)(OR⁵)₂, or HOP(O)(OR⁵)R⁵, or HOP(O)R⁵₂, wherein R⁵ is alkyl, aryl, heteroaryl, or alkenyl.

In some embodiments, LiOR² is LiOP(O)(OR⁶)₂, or LiOP(O)(OR⁶)R⁶, orLiOP(O)R⁶ ₂, wherein R⁶ is alkyl, aryl, heteroaryl, or alkenyl.

In some aspects, a molecular precursor compound can be made by ReactionScheme 5

where M is selected from Co, Mn and Ni, n is from 0 to 8, R¹ can beindependently selected, for each occurrence, from alkyl, aryl,heteroaryl, alkenyl, and silyl, the —OR² groups can be independentlyselected, for each occurrence, from alkoxy, aryloxy, heteroaryloxy,alkenyloxy, siloxy, phosphinate, phosphonate, and phosphate, and the—OR³O— groups can be as defined above.

In Reaction Scheme 5, M(NR¹ ₂)₃ is reacted with a alcohol, a diol andLiOR² to provide a molecular precursor.

In some embodiments, M(NR¹ ₂)₃ is reacted with an alcohol, a diol and alithium alkoxide to provide a molecular precursor.

[Li(OR²)₂M(OR²O)] may from a dimer or multimer, [Li(OR²)₂M(OR²O)]_(x),where x is two or more.

In some embodiments, R²OH is HOSi(OR³)₃, HOSi(OR³)₂R⁴, HOSi(OR³)R⁴ ₂, orHOSiR⁴ ₃, wherein R³ and R⁴ are independently selected from alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, LiOR² is LiOSi(OR⁴)₃, wherein R⁴ is alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, R²OH is HOP(O)(OR⁵)₂, or HOP(O)(OR⁵)R⁵, or HOP(O)R⁵₂, wherein R⁵ is alkyl, aryl, heteroaryl, or alkenyl.

In some embodiments, LiOR² is LiOP(O)(OR⁶)₂, or LiOP(O)(OR⁶)R⁶, orLiOP(O)R⁶ ₂, wherein R⁶ is alkyl, aryl, heteroaryl, or alkenyl.

In some aspects, a molecular precursor compound can be made by ReactionScheme 6

where M is selected from Co, Mn and Ni, n is from 0 to 8, R¹ can beindependently selected, for each occurrence, from alkyl, aryl,heteroaryl, alkenyl, and silyl, and the OR² groups can be independentlyselected, for each occurrence, from alkoxy, aryloxy, heteroaryloxy,alkenyloxy, siloxy, phosphinate, phosphonate, and phosphate.

In Reaction Scheme 6, M(NR¹ ₂)₃ is reacted with an alcohol and LiNR₂ toprovide a molecular precursor.

In some embodiments, M(NR¹ ₂)₂ is reacted with an alcohol and a lithiumamine to provide a molecular precursor.

In some embodiments, R²OH is HOSi(OR³)₃, HOSi(OR³)₂R⁴, HOSi(OR³)R⁴ ₂, orHOSiR⁴ ₃, wherein R³ and R⁴ are independently selected from alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, R²OH is HOP(O)(OR⁵)₂, or HOP(O)(OR⁵)R⁵, or HOP(O)R⁵₂, wherein R⁵ is alkyl, aryl, heteroaryl, or alkenyl.

In some aspects, a molecular precursor compound can be made by ReactionScheme 7

where M is selected from Co, Mn and Ni, n is from 0 to 4, and the —ORgroups can be independently selected, for each occurrence, from alkoxy,aryloxy, heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate,and phosphate.

In Reaction Scheme 7, M(OR)₂ is reacted with LiOR to provide a molecularprecursor.

In some embodiments, M(OR)₂ is reacted with a lithium alkoxide toprovide a molecular precursor.

In some embodiments, LiOR is LiOSi(OR)₃.

In some embodiments, LiOR is LiOP(O)(OR)₂, or LiOP(O)(OR)R, orLiOP(O)R₂.

In some aspects, a molecular precursor compound can be made by ReactionScheme 8

where M is selected from Co, Mn and Ni, n is from 0 to 4, and the —ORgroups can be independently selected, for each occurrence, from alkoxy,aryloxy, heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate,and phosphate.

In Reaction Scheme 8, M(OR)₃ is reacted with LiOR to provide a molecularprecursor.

In some embodiments, M(OR)₃ is reacted with a lithium alkoxide toprovide a molecular precursor.

In some embodiments, LiOR is LiOSi(OR)₃.

In some embodiments, LiOR is LiOP(O)(OR)₂, or LiOP(O)(OR)R, orLiOP(O)R₂.

In some aspects, a molecular precursor compound can be made by ReactionScheme 9

where M is selected from Co, Mn and Ni, L is a coordinating species, Xis halogen, n is from 0 to 4, and the —OR groups can be independentlyselected, for each occurrence, from alkoxy, aryloxy, heteroaryloxy,alkenyloxy, siloxy, phosphinate, phosphonate, and phosphate.

In Reaction Scheme 9, M(X)₂ is reacted with LiOR to provide a molecularprecursor.

In some embodiments, M(X)₂ is reacted with a lithium alkoxide to providea molecular precursor.

In some embodiments, LiOR is LiOSi(OR)₃.

In some embodiments, LiOR is LiOP(O)(OR)₂, or LiOP(O)(OR)R, orLiOP(O)R₂.

In some aspects, a molecular precursor compound can be made by ReactionScheme 10

where M is selected from Co, Mn and Ni, X is halogen, L is acoordinating species, n is from 0 to 8, and the —OR groups can beindependently selected, for each occurrence, from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate.

In Reaction Scheme 10, M(X)₃ is reacted with LiOR to provide a molecularprecursor.

In some embodiments, M(X)₃ is reacted with a lithium alkoxide to providea molecular precursor.

In some embodiments, LiOR is LiOSi(OR)₃.

In some embodiments, LiOR is LiOP(O)(OR)₂, or LiOP(O)(OR)R, orLiOP(O)R₂.

In the above reaction schemes, the reagent M(NR₂)₂ can be provided byreacting MX₂ with 2 equivalents of LiNR₂, NaNR₂, or KNR₂, where X ishalogen.

In the above reaction schemes, the reagent M(NR₂)₃ can be provided byreacting MX₂ with 3 equivalents of LiNR₂, NaNR₂, or KNR₂, where X ishalogen.

In some aspects, a molecular precursor compound can be made by ReactionScheme 11

where M is selected from Co, Mn and Ni, n is from 0 to 8, R¹ is alkyl,aryl, heteroaryl, alkenyl, or silyl, and the —OR² groups can beindependently selected, for each occurrence, from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate.

In Reaction Scheme 11, M(NR¹ ₂)₂ is reacted with an alcohol and LiOR² toprovide a molecular precursor.

In some embodiments, M(NR¹ ₂)₂ is reacted with an alcohol and a lithiumamine to provide a molecular precursor.

In some embodiments, R²OH is HOSi(OR³)₃, HOSi(OR³)₂R⁴, HOSi(OR³)R⁴ ₂, orHOSiR⁴ ₃, wherein R³ and R⁴ are independently selected from alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, LiOR² is LiOSi(OR⁴)₃, wherein R⁴ is alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, R²OH is HOP(O)(OR⁵)₂, or HOP(O)(OR⁵)R⁵, or HOP(O)R⁵₂, wherein R⁵ is alkyl, aryl, heteroaryl, or alkenyl.

where M is selected from Co, Mn and Ni, n is from 0 to 4, R¹ is alkyl,aryl, heteroaryl, alkenyl, or silyl, and the —OR² groups can beindependently selected, for each occurrence, from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate.

In Reaction Scheme 12, M(OR¹ ₂)₂ is reacted with an alcohol and LiNR² ₂to provide a molecular precursor.

In some embodiments, M(OR¹ ₂)₂ is reacted with an alcohol and a lithiumalkoxide to provide a molecular precursor.

In some embodiments, R²OH is HOSi(OR³)₃, HOSi(OR³)₂R⁴, HOSi(OR³)R⁴ ₂, orHOSiR⁴ ₃, wherein R³ and R⁴ are independently selected from alkyl, aryl,heteroaryl, or alkenyl.

In some embodiments, R²OH is HOP(O)(OR⁵)₂, or HOP(O)(OR⁵)R⁵, or HOP(O)R⁵₂, wherein R⁵ is alkyl, aryl, heteroaryl, or alkenyl.

Acetate Ink Compositions

Embodiments of this disclosure provide solid precursor compounds ormixtures of compounds that have surprisingly high solubility in an inkcomposition. Ink compositions of this disclosure may therefore provide ahigh throughput process for depositing cathode precursors for makingcathode materials.

The precursor compounds or mixtures of compounds that are solubilized inan ink composition of this disclosure may be selected to have thestoichiometry of a desired cathode material.

In some embodiments, precursor compounds or mixtures of compounds can besolubilized in an ink composition by mixing the precursor compounds ormixtures of compounds with one or more organic solvents.

In certain aspects, this disclosure provides precursor compounds ormixtures of compounds that are surprisingly soluble in the presence ofan acetate ink component.

Examples of an acetate ink component of this invention include alkylacetates, ethyl acetate, propyl acetate, butyl acetate, n-butyl acetate,sec-butyl acetate, tert-butyl acetate, octyl acetates, aryl acetates,alkenyl acetates, and heteroaryl acetates.

Examples of an acetate ink component of this invention include methylacetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentylacetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-nonylacetate, n-decyl acetate, n-undecyl acetate, n-dodecyl acetate,n-tridecyl acetate, n-tetradecyl acetate, n-pentadecyl acetate,n-hexadecyl acetate, n-heptadecyl acetate, and n-octadecyl acetate.

Examples of an acetate ink component of this invention include isopropylacetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate,isopentyl acetate, 2-methylbutyl acetate, 3-methylbutyl acetate,2,2-dimethylbutyl acetate, 2,3-dimethylbutyl acetate, 2-methylpentylacetate, 3-methylpentyl acetate, 4-methylpentyl acetate, 2-methylhexylacetate, 3-methylhexyl acetate, 4-methylhexyl acetate, 5-methylhexylacetate, 2,3-dimethylbutyl acetate, 2,3-dimethylpentyl acetate,2,4-dimethylpentyl acetate, 2,2-dimethylhexyl acetate, 2,3-dimethylhexylacetate, 2,4-dimethylhexyl acetate, 2,5-dimethylhexyl acetate,2,2-dimethylpentyl acetate, 3,3-dimethylpentyl acetate,3,3-dimethylhexyl acetate, 4,4-dimethylhexyl acetate, 2-ethylpentylacetate, 3-ethylpentyl acetate, 2-ethylhexyl acetate, 3-ethylhexylacetate, 4-ethylhexyl acetate, 2-methyl-2-ethylpentyl acetate,2-methyl-3-ethylpentyl acetate, 2-methyl-4-ethylpentyl acetate,2-methyl-2-ethylhexyl acetate, 2-methyl-3-ethylhexyl acetate,2-methyl-4-ethylhexyl acetate, 2,2-diethylpentyl acetate,3,3-diethylhexyl acetate, 2,2-diethylhexyl acetate, and 3,3-diethylhexylacetate.

In some embodiments, an ink composition may be formed by dissolvingprecursor compounds or mixtures of compounds in a solvent or solventmixture containing an acetate component.

The concentration of an acetate component in an ink composition of thisdisclosure may be from 0.01% to 100% (v/v), or from 1% to 99% (v/v), orfrom 1% to 50% (v/v).

In certain embodiments, an ink composition may be formed by dissolvingprecursor compounds or mixtures of compounds in an acetate component.

In further aspects, an ink composition can be made by directly formingprecursor compounds or mixtures of compounds in a solvent containing anacetate component, or in a two-component acetate-solvent mixture.

This invention can provide an ink composition in which cathode precursorcompounds or mixtures of compounds are surprisingly soluble and can beused in a high throughput process to make cathodes for lithium ionbatteries.

Ink Compositions

Embodiments of this invention further provide ink compositions whichcontain one or more molecular precursor compounds. The molecularprecursors of this invention may be used to make cathodes by printing anink containing one or more molecular precursors onto a substrate.

In some embodiments, an ink can be made by mixing a molecular precursorwith one or more solvents.

In some variations, the ink is a solution of the molecular precursors inan organic solvent. The solvent can include one or more organic liquidsor solvents, and may contain an aqueous component. A solvent may be anorganic solvent.

In certain embodiments, an ink may be a suspension or slurry of one ormore molecular precursors in an organic solvent.

An ink can be made by providing one or more molecular precursorcompounds and solubilizing, dissolving, solvating, or dispersing thecompounds with one or more solvents. The compounds dispersed in asolvent may be nanocrystalline, nanoparticles, microparticles,amorphous, or dissolved molecules.

The concentration of the molecular precursors in an ink of thisdisclosure can be from about 0.01% to about 50% (w/w), or from about0.1% to about 40%, or from about 0.1% to about 25%, or from about 1% toabout 25%, or from about 5% to about 25%.

The concentration of the molecular precursors in an ink of thisdisclosure can be from about 1% to about 99% (w/w), or from about 50% toabout 99%, or from about 50% to about 75%.

A molecular precursor may exist in a liquid or flowable phase under thetemperature and conditions used for deposition, coating or printing.

In some variations of this invention, molecular precursors that arepartially soluble, or are insoluble in a particular solvent can bedispersed in the solvent by high shear mixing.

As used herein, the term dispersing encompasses the terms solubilizing,dissolving, and solvating.

The solvent for an ink of this disclosure may be an organic liquid orsolvent. Examples of a solvent for an ink of this disclosure include oneor more organic solvents, which may contain an aqueous component.

Embodiments of this invention further provide molecular precursorcompounds having enhanced solubility in one or more solvents forpreparing inks. The solubility of a molecular precursor compound can beselected by variation of the nature and molecular size and weight of oneor more organic coordinating species attached to the compound.

An ink composition of this invention may contain any of the dopantsdisclosed herein, or a dopant known in the art.

Ink compositions of this disclosure can be made by methods known in theart, as well as methods disclosed herein.

Examples of a solvent for an ink of this disclosure include alcohol,methanol, ethanol, isopropyl alcohol, sec-butanol, thiols, butanol,butanediol, glycerols, alkoxyalcohols, glycols, 1-methoxy-2-propanol,acetone, ethylene glycol, propylene glycol, propylene glycol laurate,ethylene glycol ethers, diethylene glycol, triethylene glycolmonobutylether, propylene glycol monomethylether, 1,2-hexanediol,ethers, diethyl ether, aliphatic hydrocarbons, aromatic hydrocarbons,dodecane, hexadecane, pentane, hexane, heptane, octane, isooctane,decane, cyclohexane, p-xylene, m-xylene, o-xylene, benzene, toluene,xylene, tetrahydrofuran, 2-methyltetrahydrofuran, siloxanes,cyclosiloxanes, silicone fluids, halogenated hydrocarbons,dibromomethane, dichloromethane, dichloroethane, trichloroethanechloroform, methylene chloride, acetonitrile, esters, acetates, ethylacetate, butyl acetate, acrylates, isobornyl acrylate, 1,6-hexanedioldiacrylate, polyethylene glycol diacrylate, ketones, acetone, methylethyl ketone, cyclohexanone, butyl carbitol, cyclopentanone, lactams,N-methylpyrrolidone, N-(2-hydroxyethyl)-pyrrolidone, cyclic acetals,cyclic ketals, aldehydes, amines, diamines, amides, dimethylformamide,methyl lactate, oils, natural oils, terpenes, and mixtures thereof.

An ink of this disclosure may further include polyvinylidene fluoride.

An ink of this disclosure may further include components such as asurfactant, a dispersant, an emulsifier, an anti-foaming agent, athickener, a viscosity modifier, a flow agent, a plasticizer, anextender, a film conditioner, and an adhesion promoter. Each of thesecomponents may be used in an ink of this disclosure at a level of fromabout 0.001% to about 10% or more of the ink composition.

Examples of surfactants include siloxanes, polyalkyleneoxide siloxanes,polyalkyleneoxide polydimethylsiloxanes, polyesterpolydimethylsiloxanes, ethoxylated nonylphenols, nonylphenoxypolyethyleneoxyethanol, fluorocarbon esters, fluoroaliphatic molecularesters, fluorinated esters, alkylphenoxy alkyleneoxides, cetyl trimethylammonium chloride, carboxymethylamylose, ethoxylated acetylene glycols,betaines, N-n-dodecyl-N,N-dimethylbetaine, dialkyl sulfosuccinate salts,alkylnaphthalenesulfonate salts, fatty acid salts, polyoxyethylenealkylethers, polyoxyethylene alkylallylethers,polyoxyethylene-polyoxypropylene block copolymers, alkylamine salts,quaternary ammonium salts, and mixtures thereof.

Examples of surfactants include anionic, cationic, amphoteric, andnonionic surfactants.

A surfactant may be used in an ink of this disclosure at a level of fromabout 0.001% to about 2% of the ink composition.

Examples of a dispersant include a polymer dispersant, a surfactant,hydrophilic-hydrophobic block copolymers, acrylic block copolymers,acrylate block copolymers, graft polymers, and mixtures thereof.

Examples of an emulsifier include a fatty acid derivative, an ethylenestearamide, an oxidized polyethylene wax, mineral oils, apolyoxyethylene alkyl phenol ether, a polyoxyethylene glycol ether blockcopolymer, a polyoxyethylene sorbitan fatty acid ester, a sorbitan, analkyl siloxane polyether polymer, polyoxyethylene monostearates,polyoxyethylene monolaurates, polyoxyethylene monooleates, and mixturesthereof.

Examples of an anti-foaming agent include polysiloxanes,dimethylpolysiloxanes, dimethyl siloxanes, silicones, polyethers, octylalcohol, organic esters, ethyleneoxide propyleneoxide copolymers, andmixtures thereof.

Examples of thickeners and viscosity modifiers include celluloses,urethanes, polyurethanes, styrene maleic anhydride copolymers,polyacrylates, polycarboxylic acids, carboxymethylcelluoses,hydroxyethylcelluloses, methylcelluloses, methyl hydroxyethylcelluloses, methyl hydroxypropyl celluloses, silicas, gellants,aluminates, titanates, gums, clays, waxes, polysaccharides, starches,and mixtures thereof.

Examples of flow agents include waxes, celluloses, butyrates,surfactants, polyacrylates, and silicones.

Examples of a plasticizer include alkyl benzyl phthalates, butyl benzylphthalates, dioctyl phthalates, diethyl phthalates, dimethyl phthalates,di-2-ethylhexy-adipates, diisobutyl phthalates, diisobutyl adipates,dicyclohexyl phthalates, glycerol tribenzoates, sucrose benzoates,polypropylene glycol dibenzoates, neopentyl glycol dibenzoates, dimethylisophthalates, dibutyl phthalates, dibutyl sebacates,tri-n-hexyltrimellitates, and mixtures thereof.

In certain variations, an ink may contain a chelator, or a viscositymodifier.

In certain aspects, an ink of this disclosure may be formed as asolution, a suspension, a slurry, or a semisolid gel or paste. An inkmay include one or more molecular precursors solubilized in a solvent orsolvent mixture, or in a solvent containing an acetate component. An inkmay include one or more molecular precursors dissolved in a solvent orsolvent mixture, or in a solvent containing an acetate component, sothat the ink is a solution of the molecular precursors.

In certain variations, a molecular precursor may include particles ornanoparticles that can be suspended in a solvent or solvent mixture, orin a solvent containing an acetate component, and may be a suspension orpaint of the molecular precursors. In certain embodiments, a molecularprecursor can be mixed with a minimal amount of a solvent or solventmixture, or a solvent containing an acetate component, and may be aslurry or semisolid gel or paste of the molecular precursor.

The viscosity of an ink of this disclosure can be from about 0.5centipoises (cP) to about 50 cP, or from about 0.6 to about 30 cP, orfrom about 1 to about 15 cP, or from about 2 to about 12 cP.

The viscosity of an ink of this disclosure can be from about 20 cP toabout 2×10⁶ cP, or greater. The viscosity of an ink of this disclosurecan be from about 20 cP to about 1×10⁶ cP, or from about 200 cP to about200,000 cP, or from about 200 cP to about 100,000 cP, or from about 200cP to about 40,000 cP, or from about 200 cP to about 20,000 cP.

The viscosity of an ink of this disclosure can be about 1 cP, or about 2cP, or about 5 cP, or about 20 cP, or about 100 cP, or about 500 cP, orabout 1,000 cP, or about 5,000 cP, or about 10,000 cP, or about 20,000cP, or about 30,000 cP, or about 40,000 cP.

In some embodiments, an ink may contain one or more components from thegroup of a surfactant, a dispersant, an emulsifier, an anti-foamingagent, a thickener, a viscosity modifier, a flow agent, a plasticizer,an extender, a film conditioner, and an adhesion promoter.

An ink may be made by dispersing one or more molecular precursorcompounds of this disclosure in one or more solvents to form adispersion or solution. Molecular precursor inks may be used to formcathode layers by using multiple inks with different compositions. Theuse of multiple inks allows a wide range of compositions to bemanufactured in a controlled fashion. In some embodiments, a two inksystem is used.

Dopants

In some embodiments, the use of a molecular precursor compound caninclude a dopant.

In some embodiments, dopants may be used in solid form along withmolecular precursor compounds in solid form.

In certain embodiments, dopants may be used in solution along withmolecular precursor compounds in solution.

In further embodiments, dopants may be used in an ink composition alongwith molecular precursor compounds.

A dopant may be also introduced into a molecular precursor compound formduring the synthesis of the precursor.

A cathode material of this disclosure made from a molecular precursorcompound may contain atoms of one or more dopants.

The quantity of a dopant in an embodiment of this disclosure can be fromabout 1×10⁻⁷ atom percent to about 5 atom percent relative to the mostabundant metal atom, or greater. In some embodiments, a dopant can beincluded at a level of from about 1×10¹⁶ cm⁻³ to about 1×10²¹ cm⁻³. Adopant can be included at a level of from about 1 ppm to about 10,000ppm.

In some embodiments, a dopant may include oxides of Mg, Y, Ti, Zr, Nb,Cr, Ru, B, Al, Bi, Sb, Sn, La, and mixtures of any of the foregoing.

Dopant species can be provided from dopant source compounds Mg(OR)₂,Ti(OR)₄, Zr(OR)₄, Nb(OR)₃, Nb(OR)₅, Cr(OR)₃, Ru(OR)₃, B(OR)₃, Al(OR)₃,Sn(OR)₂, Sn(OR)₄, La(OR)₃, and mixtures of any of the foregoing, wherethe —OR groups are independently selected from alkoxy, aryloxy,heteroaryloxy, alkenyloxy, siloxy, phosphinate, phosphonate, andphosphate groups.

Any of the foregoing dopants may be used with molecular precursorcompounds in bulk solid form, or in solution, to form cathode materials.

Any of the foregoing dopant source compounds may be used in an ink orink composition of this invention. A dopant may be introduced into athin film by any of the deposition methods described herein.

Processes Using Bulk Cathode Materials

The molecular precursor compounds of this invention can be used to makebulk cathode materials by processes of this disclosure and according tomethods known in the art.

Bulk cathode materials can be used directly to make batteries.

In some embodiments, a slurry of bulk cathode material can be made frommolecular precursor compounds of this invention. The slurry may containbulk cathode material, N-Methyl-2-pyrrolidone (NMP) at 0.4 to 0.6 g/gsolids, polyvinylidene fluoride (PVDF) at 1-5%, and conductive carbon at1-5%. The slurry can be deposited on an aluminum substrate by variousmethods including knife coating and rod coating, and dried, heatedand/or pressed as required for ultimate use in battery production.

Examples of methods for depositing a slurry onto a surface or substrateinclude coating, dip coating, wet coating, spin coating, knife coating,roller coating, rod coating, slot die coating, meyerbar coating, lipdirect coating, capillary coating, liquid deposition, layer-by-layerdeposition, spin casting.

In some embodiments, a process for knife gap or die coating can beperformed. The gap can be from 1 to 1000 μm, or larger, or from 10 to1000 μm, or from 20 to 1000 μm, or from 50 to 500 μm, or from 100 to 400μm. The coating speed can be from about 5 to 100 mm/s

In some embodiments, a process for knife gap or die coating can beperformed with a thickness per pass of from 1 to 1000 micrometers, orfrom 1 to 500 micrometers, or from 1 to 200 micrometers, or from 1 to100 micrometers, or from 10 to 100 micrometers.

Processes for Thin Film Cathodes

The molecular precursor compounds of this invention can be used to makecathodes by depositing a layer onto a substrate, where the layercontains one or more molecular precursors. The deposited layer may be afilm or a thin film.

As used herein, the terms “deposit,” “depositing,” and “deposition”refer to any method for placing a compound or composition onto a surfaceor substrate, including spraying, coating, and printing.

As used herein, the term “thin film” refers to a layer of atoms ormolecules, or a composition layer on a substrate having a thickness ofless than 1000 micrometers.

Inks and ink compositions containing molecular precursor compounds ofthis invention can be deposited onto a substrate using methods disclosedherein, as well as methods known in the art.

Examples of methods for depositing onto a surface or substrate includeall forms of printing, spraying, and coating.

Cathode layers can be made by depositing one or more molecularprecursors of this disclosure on a substrate or flexible substrate in ahigh throughput roll process. The depositing of molecular precursors ina high throughput roll process can be done by printing, spraying orcoating a composition containing one or more molecular precursors ofthis disclosure.

In some aspects, the thickness of a cathode layer may be from about 0.01to about 100 micrometers, or from about 0.01 to about 20 micrometers, orfrom about 0.01 to about 10 micrometers, or from about 0.05 to about 5micrometers, or from about 0.1 to about 4 micrometers, or from about 0.1to about 3.5 micrometers, or from about 0.1 to about 3 micrometers, orfrom about 0.1 to about 2.5 micrometers.

In some embodiments, the thickness of a cathode layer may be from about1 to about 10 micrometers, or from about 1 to about 100 micrometers, orfrom about 1 to about 1000 micrometers, or from about 1 to about 500micrometers, or from about 50 to about 100 micrometers, or from about 50to about 500 micrometers, or from about 50 to about 1000 micrometers.

In some aspects, a layered substrate can be made by depositing a layerof a molecular precursor compound onto the substrate. The layer of themolecular precursor compound can be a single thin layer of the compound,or a plurality of layers of the compound.

A process to make a layered substrate can have a step of depositing asingle precursor layer of a single molecular precursor on a substrate.The precursor layer can optionally be composed of a plurality of layersof the molecular precursor compound, or of different molecular precursorcompounds. Each of the plurality of layers can be heated to form a thinfilm material layer before the deposition of the next layer of themolecular precursor compound.

The depositing of compounds by inkjet printing can be done at rates fromabout 10 nm to 3 micrometers per minute, or from 100 nm to 2 micrometersper minute.

The depositing of compounds by spraying can be done at rates from about10 nm to 3 micrometers per minute, or from 100 nm to 2 micrometers perminute.

Examples of methods for printing using an ink of this disclosure includeprinting, gravure printing, reverse gravure printing, offset gravureprinting, reverse offset gravure printing, inkjet printing, aerosol jetprinting, ink printing, jet printing, screen printing, stamp/padprinting, transfer printing, pad printing, flexographic printing,contact printing, reverse printing, thermal printing, lithography,electrophotographic printing, and combinations thereof.

Examples of methods for depositing a molecular precursor onto a surfaceor substrate include electrodepositing, electroplating, electrolessplating, bath deposition, coating, dip coating, wet coating, spincoating, knife coating, roller coating, rod coating, slot die coating,meyerbar coating, lip direct coating, capillary coating, liquiddeposition, solution deposition, layer-by-layer deposition, spincasting, and solution casting.

The molecular precursors of this invention, and ink compositionscontaining molecular precursors, can be deposited onto a substrate usingmethods known in the art, as well as methods disclosed herein.

In some embodiments, a process for knife gap or die coating can beperformed. The gap can be from 1 to 1000 μm, or larger, or from 10 to1000 μm, or from 20 to 1000 μm, or from 50 to 500 μm, or from 100 to 400μm. The coating speed can be from about 5 to 100 mm/s.

In some embodiments, a process for knife gap or die coating can beperformed with a thickness per pass of from 10 to 10,000 nanometers, orfrom 20 to 10,000 nanometers, or from 100 to 10,000 nanometers, or from100 to 5000 nanometers, or from 100 to 3000 nanometers, or from 100 to1000 nanometers.

In certain embodiments, a first molecular precursor may be depositedonto a substrate, and subsequently a second molecular precursor may bedeposited onto the substrate. In certain embodiments, several differentmolecular precursors may be deposited onto the substrate to create alayer.

In certain variations, different molecular precursors may be depositedonto a substrate simultaneously, or sequentially, whether by spraying,coating, printing, or by other methods. The different molecularprecursors may be contacted or mixed before the depositing step, duringthe depositing step, or after the depositing step. The molecularprecursors can be contacted before, during, or after the step oftransporting the molecular precursors to the substrate surface.

The depositing of molecular precursors, including by spraying, coating,and printing, can be done in a controlled or inert atmosphere, such asin dry nitrogen and other inert gas atmospheres, as well as in a partialvacuum atmosphere.

Processes for depositing, printing, spraying, or coating molecularprecursors can be done at various temperatures including from about 0°C. to about 100° C., or from about 20° C. to about 70° C.

Transforming Cathode Films or Images

Processes for making a cathode can include a step of transforming orconverting a molecular precursor compound into a material.

The step of converting a molecular precursor compound into a materialcan be performed by thermal treatment. In some embodiments, a molecularprecursor compound can be converted by the application of heat, light,kinetic, mechanical or other energy, or for example, UV light ormicrowave irradiation.

The step of converting a molecular precursor compound into a materialcan be performed at various temperatures including from about 100° C. toabout 800° C., or from about 150° C. to about 800° C., or from about200° C. to about 800° C., or from about 300° C. to about 800° C., orfrom about 400° C. to about 800° C., or from about 400° C. to about 700°C., or from about 400° C. to about 600° C., or from about 450° C. toabout 650° C., or from about 450° C. to about 600° C., or from about550° C. to about 650° C.

In some embodiments, a step of converting a molecular precursor compoundinto a material, whether performed with neat solids or in solution, canbe done with exposure to ambient air, or dry air, or air with controlledhumidity.

In some embodiments, a step of converting a molecular precursor compoundinto a material, whether performed with neat solids or in solution, canbe done in an inert atmosphere.

In certain embodiments, a step of converting a molecular precursorcompound into a material, whether performed with neat solids or insolution, can be done in an inert atmosphere after exposure of themolecular precursor compound to ambient air, or dry air, or air withcontrolled humidity.

In certain aspects, a step of converting a molecular precursor compoundinto a material, whether performed with neat solids or in solution, canbe done under oxidizing conditions or with exposure to an oxidizingatmosphere. Examples of an oxidizing atmosphere include 1% O₂/99% N₂,10% O₂/90% N₂, and air.

In certain aspects, a step of converting a mixture of molecularprecursor compounds into a material, whether performed with neat solidsor in solution, can be done under reducing conditions. Examples of areducing atmosphere include 1% H₂/99% N₂, and 5% H₂/95% N₂.

In certain aspects, depositing of molecular precursors on a substratecan be done while the substrate is heated. In these variations, acathode material may be deposited or formed directly on the substrate.

In some variations, a substrate can be cooled after a step of heating.In certain embodiments, a substrate can be cooled before, during, orafter a step of depositing a molecular precursor or ink thereof.

The step of converting a molecular precursor compound into a materialcan be performed in an inert atmosphere by heating to temperatures belowabout 400° C., or below about 300° C., or below about 200° C., or belowabout 150° C.

Embodiments of this disclosure further contemplate articles made bydepositing a layer or image onto a substrate, where the layer or imagecontains one or more molecular precursor compounds. The article may be asubstrate having a layer of a film, or a thin film, or an image which isdeposited, sprayed, coated, or printed onto the substrate. In certainvariations, an article may have a substrate printed with a molecularprecursor ink, where the ink is printed in an image pattern on thesubstrate.

After conversion of a molecular precursor compound in a layer or imageon a substrate into a material, another layer or image of the same ordifferent molecular precursor may be applied to the material on thesubstrate by repeating the deposition procedure. This process can berepeated to prepare additional material layers, or a thicker layer ofmaterial on the substrate.

Processes for making a cathode can include a step of transforming amolecular precursor compound into a material. The material can betransformed into a final product cathode material.

The step of converting a material or pre-cathode material into a cathodematerial can be performed by thermal treatment. In some embodiments, amaterial or pre-cathode material can be transformed into a final cathodematerial by annealing.

Optionally, any step of converting or annealing a molecular precursorcompound, layer, or image on a substrate can be performed underoxidizing conditions so that the molecular precursor compound istransformed to a final cathode film or material.

An annealing process may include a step of heating a substrate at atemperature sufficient to transform a material on the substrate into afinal cathode film or material.

An annealing process may include a step of heating a substrate at atemperature of from 400° C. to 800° C. for a time period of from 1 minto 60 min. In some embodiments, an annealing process includes a step ofheating a substrate at a temperature of 400° C., or 450° C., or 500° C.,or 600° C., or 650° C.

An annealing process may include a step of rapid thermal processing.

Each step of heating can transform any and all layers present on thesubstrate into a material layer.

Embodiments of this invention further provide methods and compositionsfor introducing lithium ions at a controlled concentration into variouslayers and compositions of a battery. Lithium ions can be provided invarious layers and the amount of lithium ions can be preciselycontrolled.

Devices

A schematic representation of a lithium ion battery embodiment of thisinvention is shown in FIG. 11.

The molecular precursor compounds of this invention can be used to makecathode materials for lithium ion batteries.

For example, the molecular precursor compounds of this invention can beused to make cathode materials for lithium ion batteries such as CR2032coin cell batteries, as well as pouch cell batteries.

In some embodiments, a thin film lithium ion battery device can be madefrom a cathode layer on a substrate by carrying out various finishingsteps. Finishing steps may include use of a solid or liquid electrolyte,a separator or separator materials, an anode, and packaging.

Substrates

In general, a cathode will have an adjacent current collector. Asubstrate may have an electrical contact layer or current collectorlayer on its surface. An electrical contact layer on a substrate can bea current collector for a battery or storage device.

In some embodiments, a substrate may have an adhesion layer. An adhesionlayer can be made from titanium, nickel, or chromium.

Examples of an electrical contact layer include a layer of a metal or ametal foil, as well as a layer of aluminum, copper, gold, platinum,silver, stainless steel, a metal alloy, and a combination of any of theforegoing.

Examples of substrates on which a molecular precursor of this disclosurecan be deposited or printed include insulators, glass, silicon, mica,ceramics, flexible ceramics, and combinations thereof.

Examples of substrates on which a molecular precursor of this disclosurecan be deposited or printed include metals, metal foils, aluminum,beryllium, chromium, copper, gallium, gold, lead, manganese, nickel,palladium, platinum, rhenium, rhodium, molybdenum, silver, stainlesssteel, steel, iron, strontium, tin, titanium, titanium nitride,tungsten, zinc, zirconium, metal alloys, metal silicides, metalcarbides, and combinations thereof.

Examples of substrates on which a molecular precursor of this disclosurecan be deposited or printed include the following materials on which aconductive layer has been placed: polymers, plastics, conductivepolymers, copolymers, polymer blends, polyethylene terephthalates,polycarbonates, polyesters, polyester films, mylars, polyvinylfluorides, polyvinylidene fluoride, polyethylenes, polyetherimides,polyethersulfones, polyetherketones, polyimides, polyvinylchlorides,acrylonitrile butadiene styrene polymers, silicones, epoxys, andcombinations thereof

A substrate may be layered with an adhesion promoter before thedeposition, coating or printing of a layer of a molecular precursor ofthis invention.

Examples of adhesion promoters include a glass layer, a metal layer, atitanium-containing layer, a tungsten-containing layer, atantalum-containing layer, tungsten nitride, tantalum nitride, titaniumnitride, titanium nitride silicide, tantalum nitride silicide, achromium-containing layer, a vanadium-containing layer, a nitride layer,an oxide layer, a carbide layer, and combinations thereof.

Substrates may be layered with a barrier layer before the deposition ofprinting of a layer of a molecular precursor of this invention.

Examples of a barrier layer include a glass layer, a metal layer, atitanium-containing layer, a tungsten-containing layer, atantalum-containing layer, tungsten nitride, tantalum nitride, titaniumnitride, titanium nitride silicide, tantalum nitride silicide, andcombinations thereof.

A substrate can be of any thickness, and can be from about 20micrometers to about 20,000 micrometers or more in thickness.

Target Cathode Materials

A number of target cathode materials are disclosed herein having a rangeof compositions. Methods and embodiments of this disclosure can providea wide range of target cathode materials having controlled stoichiometryof transition metal atoms.

A target cathode material may be a lithium cobalt oxide, LiCoO₂.

A target cathode material may be a lithium cobalt oxide,Li_((1+x))CoO_((2+x/2)), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

Examples of a target cathode material include Li_(1.1)CoO_(2.05),Li_(1.2)CoO_(2.01), Li_(1.3)CoO_(2.15), Li_(1.4)CoO_(2.2),Li_(1.5)CoO_(2.25), Li_(1.6)CoO_(2.3), Li_(1.7)CoO_(2.35),Li_(1.8)CoO_(2.4), Li_(1.9)CoO_(2.45), and Li₂CoO_(2.5).

A target cathode material may be a lithium manganese oxide, LiMnO₂.

A target cathode material may be a lithium manganese oxide,Li_((1+x))MnO_((2+x/2)), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

Examples of a target cathode material include Li_(1.1)MnO_(2.05),Li_(1.2)MnO_(2.01), Li_(1.3)MnO_(2.15), Li_(1.4)MnO_(2.2),Li_(1.5)MnO_(2.25), Li_(1.6)MnO_(2.3), Li_(1.7)MnO_(2.35),Li_(1.8)MnO_(2.4), Li₁₉MnO_(2.45), and Li₂MnO_(2.5).

A target cathode material may be a lithium manganese oxide, LiNiO₂.

A target cathode material may be a lithium manganese oxide,Li_((1+x))NiO_((2+x/2)), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

Examples of a target cathode material include Li_(1.1)NiO_(2.05),Li_(1.2)NiO_(2.01), Li₁₃NiO_(2.15), Li_(1.4)NiO_(2.2),Li_(1.5)NiO_(2.25), Li_(1.6)NiO_(2.3), Li_(1.7)NiO_(2.35),Li_(1.8)NiO_(2.4), Li_(1.9)NiO_(2.45), and Li₂NiO₂

A target cathode material may be a lithium cobalt phosphate, LiCoPO₄.

A target cathode material may be a lithium cobalt phosphate,Li_((1+x))Co(PO_((4+x/2))), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

Examples of a target cathode material include Li_(1.1)Co(PO_(4.05)),Li_(1.2)Co(PO_(4.1)), Li_(1.3)Co(PO_(4.15)), Li_(1.4)Co(PO_(4.2)),Li_(1.5)Co(PO_(4.25)), Li_(1.6)Co(PO_(4.3)), Li_(1.7)Co(PO_(4.35)),Li_(1.8)Co(PO_(4.4)), Li_(1.9)Co(PO_(4.45)), and Li₂Co(PO_(4.5)).

A target cathode material may be a lithium manganese phosphate, LiMnPO₄.

A target cathode material may be a lithium manganese phosphate,Li_((1+x))Mn(PO_((4+x/2))), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

Examples of a target cathode material include Li_(1.1)Mn(PO_(4.05)),Li_(1.2)Mn(PO_(4.1)), Li_(1.3)Mn(PO_(4.15)), Li_(1.4)Mn(PO_(4.2)),Li_(1.5)Mn(PO_(4.25)), Li_(1.6)Mn(PO_(4.3)), Li_(1.7)Mn(PO_(4.35)),Li_(1.8)Mn(PO_(4.4)), Li_(1.9)Mn(PO_(4.45)), and Li₂Mn(PO_(4.5)).

A target cathode material may be a lithium manganese phosphate, LiNiPO₄.

A target cathode material may be a lithium manganese phosphate,Li_((1+x))Ni(PO_((4+x/2))), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

Examples of a target cathode material include Li_(1.1)Ni(PO_(4.05)),Li_(1.2)Ni(PO_(4.1)), Li_(1.3)Ni(PO_(4.15)), Li_(1.4)Ni(PO_(4.2)),Li_(1.5)Ni(PO_(4.25)), Li_(1.6)Ni(PO_(4.3)), Li_(1.7)Ni(PO_(4.35)),Li_(1.8)Ni(PO_(4.4)), Li_(1.9)Ni(PO_(4.45)), and Li₂Ni(PO_(4.5))

A target cathode material may be a lithium cobalt silicate, Li₂CoSiO₄.

A target cathode material may be a lithium cobalt silicate,Li_((2+x))Co(SiO_((4+x/2))), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

A target cathode material may be a lithium manganese silicate,Li₂MnSiO₄.

A target cathode material may be a lithium manganese silicate,Li_((2+x))Mn(SiO_((4+x/2))), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

Examples of a target cathode material include Li_(2.1)Mn(SiO_(4.05)),Li_(2.2)Mn(SiO_(4.1)), Li_(2.3)Mn(SiO_(4.15)), Li_(2.4)Mn(SiO_(4.2)),Li_(2.5)Mn(SiO_(4.25)), Li_(2.6)Mn(SiO_(4.3)), Li_(2.7)Mn(SiO_(4.35)),Li_(2.8)Mn(SiO_(4.4)), Li_(2.9)Mn(SiO_(4.45)), and Li₃Mn(SiO_(4.5))

A target cathode material may be a lithium manganese silicate,Li₂NiSiO₄.

A target cathode material may be a lithium manganese silicate,Li_((2+x))Ni(SiO_((4+x/2))), where x is from 0 to 1. A target cathodematerial of this kind may have x from 0.01 to 1, or from 0.01 to 0.9, orfrom 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.6, or from 0.01to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.2,or from 0.01 to 0.1, or from 0.01 to 0.05. A target cathode material ofthis kind may have x equal to 0.01, or 0.05, or 0.1, or 0.2, or 0.3, or0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9.

Examples of a target cathode material include Li_(2.1)Ni(SiO_(4.05)),Li_(2.2)Ni(SiO_(4.1)), Li_(2.3)Ni(SiO_(4.15)), Li_(2.4)Ni(SiO_(4.2)),Li_(2.5)Ni(SiO_(4.25)), Li_(2.6)Ni(SiO_(4.3)), Li_(2.7)Ni(SiO_(4.35)),Li_(2.8)Ni(SiO_(4.4)), Li_(2.9)Ni(SiO_(4.45)), and Li₃Ni(SiO_(4.5))

Chemical Definitions

As used herein, the term transition metal refers to atoms of Groups 3though 12 of the Periodic Table of the elements recommended by theCommission on the Nomenclature of Inorganic Chemistry and published inIUPAC Nomenclature of Inorganic Chemistry, Recommendations 2005.

As used herein, the term atom percent, atom %, or at % refers to theamount of an atom with respect to the final material in which the atomsare incorporated. For example, “0.5 at % X in a material” refers to anamount of X atoms equivalent to 0.5 atom percent of the atoms in thematerial.

As used herein, the term (X,Y) when referring to compounds or atomsindicates that either X or Y, or a combination thereof may be found inthe formula. For example, (Ni,Co) indicates that atoms of either Ni orCo, or any combination thereof may be found. Further, using thisnotation the amount of each atom can be specified, for example, (0.75Ni,0.25 Co)

The term “alkyl” as used herein refers to a hydrocarbyl radical of asaturated aliphatic group, which can be a branched or unbranched,substituted or unsubstituted aliphatic group containing from 1 to 22carbon atoms. This definition applies to the alkyl portion of othergroups such as, for example, cycloalkyl, alkoxy, alkanoyl, aralkyl, andother groups defined below. The term “cycloalkyl” as used herein refersto a saturated, substituted or unsubstituted cyclic alkyl ringcontaining from 3 to 12 carbon atoms. As used herein, the term“C(1-5)alkyl” includes C(1)alkyl, C(2)alkyl, C(3)alkyl, C(4)alkyl, andC(5)alkyl. Likewise, the term “C(3-22)alkyl” includes C(1)alkyl,C(2)alkyl, C(3)alkyl, C(4)alkyl, C(5)alkyl, C(6)alkyl, C(7)alkyl,C(8)alkyl, C(9)alkyl, C(10)alkyl, C(11)alkyl, C(12)alkyl, C(13)alkyl,C(14)alkyl, C(15)alkyl, C(16)alkyl, C(17)alkyl, C(18)alkyl, C(19)alkyl,C(20)alkyl, C(21)alkyl, and C(22)alkyl.

As used herein, an alkyl group may be designated by a term such as Me(methyl), Et (ethyl), Pr (any propyl group), ^(n)Pr (n-Pr, n-propyl),^(i)Pr (i-Pr, isopropyl), Bu (any butyl group), ^(n)Bu (n-Bu, n-butyl),^(i)Bu (i-Bu, isobutyl), ^(s)Bu (s-Bu, sec-butyl), and ^(t)Bu (t-Bu,tert-butyl).

The term “alkoxy” as used herein refers to an alkyl, cycloalkyl,alkenyl, or alkynyl group covalently bonded to an oxygen atom. The term“alkanoyl” as used herein refers to —C(═O)-alkyl, which mayalternatively be referred to as “acyl.” The term “alkanoyloxy” as usedherein refers to —O—C(═O)-alkyl groups. The term “alkylamino” as usedherein refers to the group —NRR′, where R and R′ are each eitherhydrogen or alkyl, and at least one of R and R′ is alkyl. Alkylaminoincludes groups such as piperidino wherein R and R′ form a ring. Theterm “alkylaminoalkyl” refers to -alkyl-NRR′.

The term “aryl” as used herein refers to any stable monocyclic,bicyclic, or polycyclic carbon ring system of from 4 to 12 atoms in eachring, wherein at least one ring is aromatic. Some examples of an arylinclude phenyl, naphthyl, tetrahydro-naphthyl, indanyl, and biphenyl.Where an aryl substituent is bicyclic and one ring is non-aromatic, itis understood that attachment is to the aromatic ring. An aryl may besubstituted or unsubstituted.

The term “substituted” as used herein refers to an atom having one ormore substitutions or substituents which can be the same or differentand may include a hydrogen substituent. Thus, the terms alkyl,cycloalkyl, alkenyl, alkynyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino,alkylaminoalkyl, aryl, heteroaryl, heterocycle, aroyl, and aralkyl asused herein refer to groups which include substituted variations.Substituted variations include linear, branched, and cyclic variations,and groups having a substituent or substituents replacing one or morehydrogens attached to any carbon atom of the group. Substituents thatmay be attached to a carbon atom of the group include alkyl, cycloalkyl,alkenyl, alkynyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino,alkylaminoalkyl, aryl, heteroaryl, heterocycle, aroyl, aralkyl, acyl,hydroxyl, cyano, halo, haloalkyl, amino, aminoacyl, alkylaminoacyl,acyloxy, aryloxy, aryloxyalkyl, mercapto, nitro, carbamyl, carbamoyl,and heterocycle. In general, a substituent may itself be furthersubstituted with any atom or group of atoms.

Some examples of a substituent for a substituted alkyl include halogen,hydroxyl, carbonyl, carboxyl, ester, aldehyde, carboxylate, formyl,ketone, thiocarbonyl, thioester, thioacetate, thioformate,selenocarbonyl, selenoester, selenoacetate, selenoformate, alkoxyl,phosphoryl, phosphonate, amino, amido, amidine, imino, cyano, nitro,azido, carbamato, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl,sulfonamido, sulfonyl, silyl, heterocyclyl, aryl, aralkyl, aromatic, andheteroaryl.

It will be understood that “substitution” or “substituted with” refersto such substitution that is in accordance with permitted valence of thesubstituted atom and the substituent. As used herein, the term“substituted” includes all permissible substituents.

This invention encompasses any and all tautomeric, solvated orunsolvated, hydrated or unhydrated forms, as well as any atom isotopeforms of the compounds and compositions disclosed herein.

This invention encompasses any and all crystalline polymorphs ordifferent crystalline forms of the compounds and compositions disclosedherein.

Additional Embodiments

All publications, references, patents, patent publications and patentapplications cited herein are each hereby specifically incorporated byreference in their entirety for all purposes.

While this invention has been described in relation to certainembodiments, aspects, or variations, and many details have been setforth for purposes of illustration, it will be apparent to those skilledin the art that this invention includes additional embodiments, aspects,or variations, and that some of the details described herein may bevaried considerably without departing from this invention. Thisinvention includes such additional embodiments, aspects, and variations,and any modifications and equivalents thereof. In particular, thisinvention includes any combination of the features, terms, or elementsof the various illustrative components and examples.

The use herein of the terms “a,” “an,” “the” and similar terms indescribing the invention, and in the claims, are to be construed toinclude both the singular and the plural.

The terms “comprising,” “having,” “include,” “including” and“containing” are to be construed as open-ended terms which mean, forexample, “including, but not limited to.” Thus, terms such as“comprising,” “having,” “include,” “including” and “containing” are tobe construed as being inclusive, not exclusive.

Recitation of a range of values herein refers individually to each andany separate value falling within the range as if it were individuallyrecited herein, whether or not some of the values within the range areexpressly recited. For example, the range “4 to 12” includes withoutlimitation any whole, integer, fractional, or rational value greaterthan or equal to 4 and less than or equal to 12, as would be understoodby those skilled in the art. Specific values employed herein will beunderstood as exemplary and not to limit the scope of the invention.

Recitation of a range of a number of atoms herein refers individually toeach and any separate value falling within the range as if it wereindividually recited herein, whether or not some of the values withinthe range are expressly recited. For example, the term “C1-8” includeswithout limitation the species C1, C2, C3, C4, C5, C6, C7, and C8.

Definitions of technical terms provided herein should be construed toinclude without recitation those meanings associated with these termsknown to those skilled in the art, and are not intended to limit thescope of the invention. Definitions of technical terms provided hereinshall be construed to dominate over alternative definitions in the artor definitions which become incorporated herein by reference to theextent that the alternative definitions conflict with the definitionprovided herein.

The examples given herein, and the exemplary language used herein aresolely for the purpose of illustration, and are not intended to limitthe scope of the invention. All examples and lists of examples areunderstood to be non-limiting.

When a list of examples is given, such as a list of compounds, moleculesor compositions suitable for this invention, it will be apparent tothose skilled in the art that mixtures of the listed compounds,molecules or compositions may also be suitable.

EXAMPLES Molecular Precursor Compounds Example 1 Cathode MolecularPrecursor Compound LiMn(O^(t)Bu)₃

A cathode molecular precursor compound represented by the formulaLiMn(O^(t)Bu)₃ was synthesized using the following procedure.

To a light brown solution of LiN(SiMe₃)₂ (0.50 g, 3.0 mmol) andMn[N(SiMe₃)₂]₂ (1.13 g, 3.0 mmol) in 30 mL THF was added ^(t)BuOH (0.90mL, 9.5 mmol) using a syringe under inert atmosphere (Schlenk line). Thereaction mixture remained light brown in color. The reaction mixture wasstirred at 25° C. for 12 h, followed by filtration and removal of thevolatile species (solvent and HN(SiMe₃)₂) under dynamic vacuum. 0.67 gof product (80%) was isolated as a beige solid.

Example 2 Cathode Molecular Precursor Compound LiMn(O^(s)Bu)₃

A cathode molecular precursor compound represented by the formulaLiMn(O^(s)Bu)₃ was synthesized using the following procedure.

To a light brown solution of LiN(SiMe₃)₂ (0.91 g, 5.4 mmol) andMn[N(SiMe₃)₂]₂ (2.05 g, 5.4 mmol) in 60 mL THF was added ^(s)BuOH (1.60mL, 17.4 mmol) using a syringe under inert atmosphere (Schlenk line).The reaction mixture slowly changed color to pink/brown in 30 min. Thereaction mixture was stirred at 25° C. for 12 h, followed by filtrationand removal of the volatile species (solvent and HN(SiMe₃)₂) underdynamic vacuum. 0.92 g of product (61%) was recovered as a brown solid.

Elemental analysis by ICP: Li to Mn ratio, 1.00:1.00.

Elemental analysis by combustion (wt %): C, 50.61, H, 9.60.

Example 3 Cathode Molecular Precursor Compound Li₂Mn(O^(s)Bu)₄

A cathode molecular precursor compound represented by the formulaLi₂Mn(O^(s)Bu)₄ was synthesized using the following procedure.

To an orange solution of LiN(SiMe₃)₂ (0.84 g, 5.0 mmol) andMn[N(SiMe₃)₂]₂ (0.95 g, 2.5 mmol) in 100 mL THF was added ^(s)BuOH (1.2mL, 13 mmol) via syringe under inert atmosphere (Schlenk line). Thelight brown reaction mixture was stirred at 25° C. for 12 h, followed byfiltration and removal of volatiles under reduced pressure. 0.53 g ofproduct (59%) was recovered as a brown solid.

The Li/Mn ratio was found to be 2.14:1.00 by use of ICP analysis.

Example 4 Cathode Molecular Precursor Compound LiNi(O^(s)Bu)₃

A cathode molecular precursor compound represented by the formulaLiNi(O^(s)Bu)₃ was synthesized using the following procedure.

To a 100 mL Schlenk flask was added LiN(SiMe₃)₂ (0.47 g, 2.8 mmol),Ni(O^(s)Bu)₂ (0.58 g, 2.8 mmol) and 60 mL THF. The reaction mixture wasstirred at 60° C. for 1 hr resulting in a dark brown homogeneoussolution. The reaction mixture was then cooled to 25° C., followed byaddition of ^(s)BuOH (0.30 mL, 3.3 mmol) via syringe under inertatmosphere (Schlenk line). The reaction mixture remained dark brown andwas stirred at 25° C. for 12 h, followed by filtration and removal ofvolatiles under reduced pressure. 0.46 g of product (58%) was recoveredas a glassy black solid.

Example 5 Cathode Molecular Precursor Compound Li₂Co(O^(s)Bu)₄

A cathode molecular precursor compound represented by the formulaLi₂Co(O^(s)Bu)₄ was synthesized using the following procedure.

To an orange solution of LiN(SiMe₃)₂ (1.47 g, 8.8 mmol) andCo[N(SiMe₃)₂]₂ (1.67 g, 4.4 mmol) in 100 mL THF was added ^(s)BuOH (1.8mL, 20 mmol) via syringe under inert atmosphere (Schlenk line). Thereaction mixture changed color from green to purple and was stirred at25° C. for 12 h, followed by filtration and removal of the volatilesunder reduced pressure. 1.28 g of product (80%) was recovered as apurple solid.

The Li/Co ratio was measured as 1.87:1.00 by use of ICP analysis.

Example 6 Cathode Molecular Precursor Compound LiCo[OP(O)(O^(t)Bu)₂]₃

A cathode molecular precursor compound represented by the formulaLiCo[OP(O)(O^(t)Bu)₂]₃ was synthesized using the following procedure.

To a deep green solution of LiN(SiMe₃)₂ (0.38 g, 2.3 mmol) andCo[N(SiMe₃)₂]₂ (0.86 g, 2.3 mmol) in 60 mL THF was added(^(t)BuO)₂P(O)OH (1.43 g, 6.8 mmol) at −35° C. under inert atmosphere ina glovebox. The reaction mixture rapidly changed color to blue and wasallowed to stir at 25° C. for 12 h. A blue solid precipitated from thesolution after stirring. The reaction mixture was filtered and theresidual solid product was washed with 30 mL of pentane, dried underreduced pressure, and isolated (total 0.81 g; 51% yield).

The Li/Co/P ratio was measured as 1.06:1.00:3.32 by use of ICP analysis.

Example 7 Cathode Molecular Precursor Compound LiCo(OEt)₃

A cathode precursor compound represented by the formula[LiCo(OEt)₃].0.25THF was synthesized using the following procedure.

To a dark green solution of LiN(SiMe₃)₂ (0.44 g, 2.63 mmol) andCo[N(SiMe₃)₂]₂ (1.01 g, 2.63 mmol) in 50 mL THF was added EtOH (0.47 mL,7.9 mmol) using a syringe under inert atmosphere (Schlenk line). Thereaction mixture rapidly changed color to dark blue and was allowed tostir at 25° C. for 12 h, followed by filtration and removal of volatilesolvent and HN(SiMe₃)₂ under dynamic vacuum. 0.25 g of compound wasrecovered as a dark blue solid, 40% yield.

Example 8 Cathode Molecular Precursor Compound LiCo(O^(i)Pr)₃

A cathode precursor compound represented by the formula[LiCo(O^(i)Pr)₃].0.125THF was synthesized using the following procedure.

To a dark green solution of LiN(SiMe₃)₂ (0.90 g, 5.3 mmol) andCo[N(SiMe₃)₂]₂ (2.04 g, 5.3 mmol) in 80 mL THF was added ¹PrOH (1.22 mL,15.9 mmol) using a syringe under inert atmosphere (Schlenk line). Thereaction mixture rapidly changed color to dark purple and was allowed tostir at 25° C. for 12 h, followed by filtration and removal of volatilesolvent and HN(SiMe₃)₂ under dynamic vacuum. 0.92 g of compound wasrecovered as a purple solid, 66% yield.

Example 9 Cathode Molecular Precursor Compound LiCo(O^(s)Bu)₃

A cathode molecular precursor compound represented by the formula[LiCo(O^(s)Bu)₃] was synthesized using the following procedure.

To a dark green solution of LiN(SiMe₃)₂ (2.36 g, 14.1 mmol) andCo[N(SiMe₃)₂]₂ (5.35 g, 14.1 mmol) in 60 mL THF was added ^(s)BuOH (3.85mL, 42.3 mmol) using a syringe under inert atmosphere (Schlenk line).The reaction mixture rapidly changed color to dark purple and wasallowed to stir at 25° C. for 12 h, followed by filtration and removalof volatile solvent and HN(SiMe₃)₂ under dynamic vacuum. 3.41 g ofcompound was recovered as a purple solid, 85% yield.

Example 10 Cathode Molecular Precursor Compound LiCo(O^(n)Bu)₃

A cathode molecular precursor compound represented by the formula[LiCo(O^(n)Bu)₃] was synthesized using the following procedure.

To a dark green solution of LiN(SiMe₃)₂ (0.26 g, 1.6 mmol) andCo[N(SiMe₃)₂]₂ (0.59 g, 1.6 mmol) in 20 mL THF was added ^(n)BuOH (0.43mL, 4.8 mmol) using a syringe under inert atmosphere (Schlenk line). Thereaction mixture rapidly changed color to dark blue/purple and wasallowed to stir at 25° C. for 12 h, followed by filtration and removalof volatile solvent and HN(SiMe₃)₂ under dynamic vacuum. 0.27 g ofcompound was recovered as a blue solid, 59% yield.

Example 11 Cathode Molecular Precursor Compound LiCo(O^(t)Bu)₃

A cathode molecular precursor compound represented by the formula[LiCo(O^(t)Bu)₃].2THF was synthesized using the following procedure.

To a dark green solution of LiN(SiMe₃)₂ (0.50 g, 3.0 mmol) andCo[N(SiMe₃)₂]₂ (1.13 g, 3.0 mmol) in 60 mL THF was added ^(t)BuOH (0.85mL, 9.0 mmol) using a syringe under inert atmosphere (Schlenk line). Thereaction mixture rapidly changed color to dark purple and was allowed tostir at 25° C. for 12 h, followed by filtration and removal of volatilesolvent and HN(SiMe₃)₂ under dynamic vacuum. 0.71 g of compound wasrecovered as a purple solid, 55% yield.

Bulk Cathode Materials Example 12 Bulk Cathode Material from MolecularPrecursor Compound LiMn(O^(t)Bu)₃

The molecular precursor compound LiMn(O^(t)Bu)₃ was converted into bulkcathode material lithium manganese oxide. 0.10 g of LiMn(O^(t)Bu)₃ wasconverted into bulk material by heating at 300° C. in a tube furnace inair for 10 minutes. A ceramic yield of 33.8% was observed, compared tothe theoretical yield of 33.4% for LiMnO₂.

The Li/Mn ratio was measured as 0.89:1.00 by use of ICP analysis.

Example 13 Bulk Cathode Material from Molecular Precursor CompoundLiMn(O^(s)Bu)₃

The molecular precursor compound LiMn(O^(s)Bu)₃ was converted into bulkcathode material lithium manganese oxide. 0.10 g of LiMn(O^(s)Bu)₃ wasconverted into bulk material by heating at 300° C. in a tube furnace inair for 10 minutes. A ceramic yield of 36.6% was observed, compared tothe theoretical yield of 33.4% for LiMnO₂.

The Li/Mn ratio was measured as 0.94:1.00 by use of ICP analysis.

Example 14 Bulk Cathode Material from Molecular Precursor CompoundLi₂Mn(O^(s)Bu)₄

The molecular precursor compound Li₂Mn(O^(s)Bu)₄ was converted into bulkcathode material lithium manganese oxide. 0.10 g of Li₂Mn(O^(s)Bu)₄ washeated at 300° C. in a tube furnace in air for 10 minutes. A ceramicyield of 35.4% was observed, compared to the theoretical yield of 29.8%for Li₂MnO_(2.5).

Elemental analysis of bulk material by ICP: The Li/Mn ratio was found tobe 1.73:1.00.

Example 15 Bulk Cathode Material from Molecular Precursor CompoundLiNi(O^(s)Bu)₃

The molecular precursor compound LiNi(O^(s)Bu)₃ was converted into bulkcathode material lithium manganese oxide. 0.10 g of LiNi(O^(s)Bu)₃ washeated at 300° C. in a tube furnace in air for 10 minutes. A ceramicyield of 35.7% was observed, compared to the theoretical yield of 33.4%for LiNiO₂.

Example 16 Bulk Cathode Material from Molecular Precursor CompoundLi₂Co(O^(s)Bu)₄

The molecular precursor compound Li₂Co(O^(s)Bu)₄ was converted into bulkcathode material lithium cobalt oxide. 0.10 g of Li₂Co(O^(s)Bu)₄ washeated at 300° C. in a tube furnace in air for 10 minutes. A ceramicyield of 36.7% was observed, compared to the theoretical yield of 30.9%for Li₂CoO_(2.5).

The Li/Mn ratio was measured as 1.97:1.00 by use of ICP analysis.

Example 17 Bulk Cathode Material from Molecular Precursor Compound[LiCo(OEt)₃]

The molecular precursor compound [LiCo(OEt)₃].0.25THF was converted intobulk cathode material lithium cobalt oxide. 0.10 g of[LiCo(OEt)₃].0.25THF was heated at 500° C. on a hot plate in air. Aceramic yield of 42.3% was observed, as compared to a theoretical yieldfor LiCoO₂ of 42.3% (w/w).

Example 18 Bulk Cathode Material from Molecular Precursor Compound[LiCo(O^(i)Pr)₃]

The molecular precursor compound [LiCo(O^(i)Pr)₃].0.125THF was convertedinto bulk cathode material lithium cobalt oxide. 0.10 g of[LiCo(O^(i)Pr)₃].0.125THF was heated at 500° C. on a hot plate in air. Aceramic yield of 37.8% (w/w) was observed, as compared to a theoreticalyield for LiCoO₂ of 38.0% (w/w).

Example 19 Bulk Cathode Material from Molecular Precursor CompoundLiCo(O^(s)Bu)₃

The molecular precursor compound LiCo(O^(s)Bu)₃ was converted into bulkcathode material lithium cobalt oxide. 0.10 g of LiCo(O^(s)Bu)₃ washeated at 500° C. on a hot plate in air. A ceramic yield of 33.7% (w/w)was observed, as compared to a theoretical yield for LiCoO₂ of 34.4%(w/w).

FIG. 2 shows the X-ray diffraction pattern of a bulk material LiCoO₂prepared from the cathode molecular precursor compound LiCo(O^(s)Bu)₃that was annealed in a tube furnace at 650° C.

Example 20 Bulk Cathode Material from Molecular Precursor CompoundLiCo(O^(n)Bu)₃

The molecular precursor compound LiCo(O^(n)Bu)₃ was converted into bulkcathode material lithium cobalt oxide. 0.10 g of LiCo(O^(n)Bu)₃ washeated at 500° C. on a hot plate in air. A ceramic yield of 36.1% (w/w)was observed, as compared to a theoretical yield for LiCoO₂ of 34.4%(w/w).

Example 21 Bulk Cathode Material from Molecular Precursor CompoundLiCo(O^(t)Bu)₃

The molecular precursor compound [LiCo(O^(t)Bu)₃].2THF was convertedinto bulk cathode material lithium cobalt oxide. 0.10 g of[LiCo(O^(t)Bu)₃].2THF was heated at 500° C. on a hot plate in air. Aceramic yield of 23.5% (w/w) was observed, as compared to a theoreticalyield for LiCoO₂ of 22.8% (w/w).

ICP analysis of the material after conversion showed the Li to Co atomicratio as being 1 to 1, Li/Co=1.

Ink Compositions Example 22 Ink Compositions of Cathode MolecularPrecursor Compound LiCo(O^(s)Bu)₃

Inks were made according to the following procedures.

-   (a) An ink was prepared by dissolving 0.15 g of the cathode    precursor compound [LiCo(O^(s)Bu)₃] in n-butyl acetate to a    concentration of 5 wt %. The resulting ink was filtered through a    0.2 μm syringe filter prior to use.-   (b) An ink was prepared by dissolving 0.15 g of the cathode    precursor compound [LiCo(O^(s)Bu)₃] in n-butyl acetate to a    concentration of 10 wt %. The resulting ink was filtered through a    0.2 μm syringe filter prior to use.-   (c) An ink was prepared by dissolving 1.0 g of the cathode precursor    compound [LiCo(O^(s)Bu)₃] in n-butyl acetate to a concentration of    10 wt %. The resulting ink was filtered through a 0.2 μm syringe    filter prior to use.-   (d) An ink was prepared by dissolving 0.33 g of the cathode    precursor compound [LiCo(O^(s)Bu)₃] in n-butyl acetate to a    concentration of 15 wt %. The resulting ink was filtered through a    0.2 μm syringe filter prior to use.-   (e) An ink was prepared by dissolving 0.15 g of the cathode    precursor compound [LiCo(O^(s)Bu)₃] in n-butyl acetate to a    concentration of 20 wt %. The resulting ink was filtered through a    0.2 μm syringe filter prior to use.-   (f) An ink was prepared by dissolving 0.15 g of the cathode    precursor compound [LiCo(O^(s)Bu)₃] in ethyl acetate to a    concentration of 10 wt %. The resulting ink was filtered through a    0.2 μm syringe filter prior to use.

Example 23 Ink Compositions of Cathode Molecular Precursor Compounds

Inks were made according to the following procedures.

(1) A blue/purple solution of LiCo(O^(s)Bu)₃ was prepared by dissolving0.30 g of the molecule in 2.70 g of n-butyl acetate at room temperature(10 wt % molecule).(2) A dark brown solution of LiMn(O^(s)Bu)₃ was prepared by dissolving0.30 g of the molecule in 2.70 g of n-butyl acetate at room temperature(10 wt % molecule).(3) A purple solution of Li₂Co(O^(s)Bu)₄ was prepared by dissolving 0.30g of the molecule in 2.70 g of 2-methyl tetrahydrofuran at roomtemperature (10 wt % molecule).(4) A brown solution of Li₂Mn(O^(s)Bu)₄ was prepared by dissolving 0.30g of the molecule in 2.70 g of 2-methyl tetrahydrofuran at roomtemperature (10 wt % molecule).

Example 24 Ink Compositions of Cobalt Cathode Molecular PrecursorCompounds

Inks were made according to the following procedures.

(1) An ink was prepared by dissolving 0.15 g of the cathode precursorcompound [LiCo(O^(i)Pr)₃].0.125THF in n-butyl acetate to a concentrationof 10 wt %.(2) An ink was prepared by dissolving 0.15 g of the cathode precursorcompound [LiCo(O^(i)Pr)₃].0.125THF in ethyl acetate to a concentrationof 10 wt %.(3) A cathode molecular precursor ink was prepared by dissolving 0.33 gof LiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.(4) A cathode molecular precursor ink was prepared by dissolving 0.33 gof LiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.(5) A cathode molecular precursor ink was prepared by dissolving 0.33 gof LiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.

Example 25 Inks of LiCo(O^(s)Bu)₃ with Binary Solvent Systems

Cathode precursor inks were made according to the following proceduresusing binary or two-solvent systems. The resulting ink may be filteredthrough a 0.2 μm syringe filter prior to use.

An ink was prepared by adding 0.08 g of n-butyl acetate to a mixture of0.15 g of the cathode precursor compound [LiCo(O^(s)Bu)₃] and2-methyl-tetrahydrofuran. The ink had a concentration of 10 wt % of thecathode precursor compound.

An ink was prepared by adding 0.15 g of the cathode precursor compound[LiCo(O^(s)Bu)₃] to a 50:50 butyl acetate/N-methylpyrrolidone mixture toa concentration of 10 wt % of the cathode precursor compound.

An ink was prepared by adding 0.15 g of the cathode precursor compound[LiCo(O^(s)Bu)₃] to a 50:50 butyl acetate/2-methyl-tetrahydrofuranmixture to a concentration of 10 wt % of the cathode precursor compound.

An ink was prepared by adding 0.09 g of the cathode precursor compound[LiCo(O^(s)Bu)₃] to a 50:50 butyl acetate/dodecane mixture to aconcentration of 10 wt % of the cathode precursor compound.

An ink was prepared by adding 0.18 g of n-butyl acetate to a mixture of0.11 g of the cathode precursor compound [LiCo(O^(s)Bu)₃] and 1.72 gcyclohexane. The ink had a concentration of 5.5 wt % of the cathodeprecursor compound.

An ink was prepared by adding 0.1 g of the cathode precursor compound[LiCo(O^(s)Bu)₃] to 0.2 g n-butyl acetate to which 1.7 g of heptanes wasadded, giving a concentration of 5 wt % of the cathode precursorcompound.

Processes for Cathode Materials by Deposition of Films of MolecularPrecursor Compounds Example 26 Inkjet Printing of Cathode MolecularPrecursor Inks

Cathode precursor inks were prepared by dissolving 0.15 g of the cathodeprecursor compound [LiCo(O^(s)Bu)₃] in n-butyl acetate to aconcentration of 5 wt %, 10 wt %, 15 wt % and 20 wt % of the cathodeprecursor compound.

The cathode precursor inks were printed onto a current collector coatedsubstrate by inkjet printing with a Fujifilm Dimatix DMP-2831 inkjetprinter. Films having a thickness from 1 to 2 micrometers were made.

Example 27 Cathode Thin Film Prepared by Inkjet Printing

A cathode molecular precursor ink was prepared by dissolving 0.33 g ofLiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.

The cathode molecular precursor ink of LiCo(O^(s)Bu)₃ was printed onto acurrent collector coated substrate via inkjet printing (Fujifilm DimatixDMP-2831 inkjet printer) with 3 wet passes of the pattern per layer and50% overlap line-to-line. Each layer was heated at 400° C. for 10minutes under inert atmosphere. A total of 16 layers were coated.Annealing of the cathode film was done at 500° C. for 10 minutes in dryair. The cathode film had an average thickness of ˜2.8 μm, as determinedby use of cross-section SEM analysis. The Li/Co stoichiometry wasdetermined to be 1.01:1.00 by use of ICP analysis.

Example 28 Cathode Thin Film Prepared by Inkjet Printing

A cathode molecular precursor ink was prepared by dissolving 0.33 g ofLiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.

The cathode molecular precursor ink of LiCo(O^(s)Bu)₃ was printed onto acurrent collector coated substrate via inkjet printing (Fujifilm DimatixDMP-2831 inkjet printer) with 3 wet passes of the pattern per layer and53% overlap line-to-line. 8 total layers were coated. Each layer washeated at 200° C. for 5 minutes under inert atmosphere followed by onefinal heat treatment at 200° C. in air for 15 minutes. The Li/Costoichiometry was determined to be 0.93:1.00 by use of ICP analysis.

Example 29 Cathode Thin Film Prepared by Inkjet Printing

A cathode molecular precursor ink was prepared by dissolving 0.33 g ofLiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.

The cathode molecular precursor ink of LiCo(O^(s)Bu)₃ was printed onto acurrent collector coated substrate via inkjet printing (Fujifilm DimatixDMP-2831 inkjet printer) with 1 wet passes of the pattern per layer and50% overlap line-to-line. Each layer was dried at 100° C. for 3 minutesunder inert atmosphere, exposed to air at 25° C. for 3 minutes, andsubsequently heated at 400° C. for 5 minutes under inert atmosphere. Atotal of 9 layers were coated. Annealing of the cathode film was done at500° C. for 3 minutes in dry air with a ramp rate of 2° C./s. Thecathode film had an average thickness of ˜0.50 μm, as determined by useof cross-section SEM analysis. The Li/Co stoichiometry was determined tobe 1.11:1.00 by use of ICP analysis.

Example 30 Cathode Thin Film Prepared by Inkjet Printing

A cathode molecular precursor ink was prepared by dissolving 0.15 g ofLiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 10 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.

The cathode molecular precursor ink of LiCo(O^(s)Bu)₃ was printed onto acurrent collector coated substrate via inkjet printing (Fujifilm DimatixDMP-2831 inkjet printer) with 6 wet passes of the pattern per layer and0% overlap line-to-line. Each layer was dried in vacuum at 25° C. for 5minutes and heated at 500° C. for 10 minutes under inert atmosphere. Atotal of 16 layers were coated. Annealing of the cathode film was doneat 500° C. for 3 minutes in dry air with a ramp rate of 2° C./s.

The Raman scattering spectrum (Evans Analytical Group) for this thinfilm of LiCoO₂ cathode is shown in FIG. 3. FIG. 3 shows the presence ofthe desired high temperature layered LiCoO₂ crystalline phase (˜485 cm⁻¹and ˜595 cm⁻¹) without significant peaks for the less desiredlow-temperature spinel phase (˜520 cm⁻¹ and ˜690 cm⁻¹).

Example 31 Cathode Thin Film Prepared by Inkjet Printing

A cathode molecular precursor ink was prepared by dissolving 0.33 g ofLiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.

The cathode molecular precursor ink of LiCo(O^(s)Bu)₃ was printed onto acurrent collector coated substrate via inkjet printing (Fujifilm DimatixDMP-2831 inkjet printer) with 1 wet pass of the pattern per layer and50% overlap line-to-line. Each layer was dried at 100° C. for 3 minutesunder inert atmosphere and heated at 300° C. for 5 minutes in air. Atotal of 14 layers were coated. Annealing of the cathode film was doneat 580° C. for 3 minutes in dry air with a ramp rate of 2° C./s.

The Raman scattering spectrum (Evans Analytical Group) for this thinfilm of LiCoO₂ cathode is shown in FIG. 4. FIG. 4 shows the presence ofthe desired high temperature layered LiCoO₂ crystalline phase (˜485 cm⁻¹and ˜595 cm⁻¹) without significant peaks for the less desiredlow-temperature spinel phase (˜520 cm⁻¹ and 690 cm⁻¹).

Example 32 Spray Deposition of a LiCoO₂ Cathode Material

A cathode molecular precursor ink was prepared by dissolving 0.33 g ofLiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt % followedby dilution of an aliquot of the ink via addition of an equal volume ofn-butyl acetate. The resulting ink was filtered through a 0.2 μm syringefilter prior to use.

The cathode molecular precursor ink was spray coated onto a 0.1 mm thickTi foil substrate coated with a thin layer of Pt using a spray coatingsystem consisting of a JKEM syringe pump for ink delivery, a nitrogengas supply source, and a standard spray head. The spray head wasrastered over a 2×2 inch area with an 18 mm overspray at each edge. TheN₂ gas pressure was set to 20 psi and the rate of liquid injection was0.68 mL/min. A total of 4 layers of ink were deposited. Each layer wasdried at 100° C. for 3 minutes, exposed to air at 25° C. for 1 minute,and then heated at 300° C. for 5 minutes in inert atmosphere. The finalconverted film was annealed at 500° C. for 3 minutes in clean dry air.

The Li/Co ratio of the LiCoO₂ film was 1.18:1.00 by use of ICP analysis.

Example 33 Slurry Coating of a LiCoO₂ Cathode Material Formed from aMolecular Precursor

A LiCoO₂ cathode material was prepared by heating 2.11 grams ofLiCo(O^(s)Bu)₃ in a tube furnace in air at 300° C. for 30 minutes. Theresultant 0.8 g of black powder was then annealed in air at 700° C. for12 hours and subsequently ground into a fine powder using a mortar andpestle. 0.3 g of the powder was combined with 0.007 g of polyvinylidenefluoride (PVDF, Aldrich), 0.006 g of carbon black (Super P, Alfa Aesar)and 0.52 g of 1-methyl-2-pyrrolidone (NMP, Aldrich). The materials weremixed in a Thinky AR-100 planetary centrifugal mixer at 1000 RPM eighttimes for 5 minutes per mix cycle to form a slurry paste. The resultantslurry was coated onto an aluminum substrate using an RK K202 knifecoater with a gap of 200 μm and a speed of 150 cm/min. This LiCoO₂coated aluminum foil can be used to form a battery device.

Example 34 Cathode Material Prepared by Spin Coating

An ink containing 50 mol % LiCo(O^(s)Bu)₃ and 50 mol % Li₂Co(O^(s)Bu)₄was prepared by mixing 0.285 g of solution “1” and 0.365 g of solution“3”. The final cathode material target for this ink wasLi_(1.5)CoO_(2.25). The ink was spin coated (SCS Spincoat G3P-8) onto a50×50×0 7 mm glass substrate with a 1300 rpm spin rate and 40 s spintime under an inert atmosphere (glove box) and dried at 100° C. for 3minutes leaving a molecular precursor film. The substrate was thenheated in air at 300° C. for 5 minutes to form a Li_(1.5)CoO_(2.25)cathode film with a thickness of 120 nm.

The Li/Co ratio was found to be 1.70:1.00 by use of ICP.

Solution 1. A blue/purple solution of LiCo(O^(s)Bu)₃ was prepared bydissolving 0.30 g of the molecule in 2.70 g of n-butyl acetate at roomtemperature (10 wt % molecule).

Solution 2. A dark brown solution of LiMn(O^(s)Bu)₃ was prepared bydissolving 0.30 g of the molecule in 2.70 g of n-butyl acetate at roomtemperature (10 wt % molecule).

Solution 3. A purple solution of Li₂Co(O^(s)Bu)₄ was prepared bydissolving 0.30 g of the molecule in 2.70 g of 2-methyl tetrahydrofuranat room temperature (10 wt % molecule).

Solution 4. A brown solution of Li₂Mn(O^(s)Bu)₄ was prepared bydissolving 0.30 g of the molecule in 2.70 g of 2-methyl tetrahydrofuranat room temperature (10 wt % molecule).

Example 35 Cathode Material Prepared by Spin Coating

An ink containing 80 mol % LiCo(O^(s)Bu)₃ and 20 mol % Li₂Co(O^(s)Bu)₄was prepared by mixing 0.428 g of solution “1” and 0.137 g of solution“3”. The final cathode material target for this ink wasLi_(1.2)CoO_(2.1). The ink was spin coated (SCS Spincoat G3P-8) onto a50×50×0 7 mm glass substrate with a 1300 rpm spin rate and 40 s spintime under an inert atmosphere (glove box) and dried at 100° C. for 3minutes leaving a molecular precursor film. The substrate was thenheated in air at 300° C. for 5 minutes to form a Li_(1.2)CoO_(2.1)cathode film with a thickness of 120 nm.

The Li/Co ratio was found to be 1.07:1.00 by use of ICP.

Example 36 Cathode Material Prepared by Spin Coating

An ink containing 50 mol % LiMn(O^(s)Bu)₃ and 50 mol % Li₂Mn(O^(s)Bu)₄was prepared by mixing 0.281 g of solution “2” and 0.361 g of solution“4”. The final cathode material target for this ink wasLi_(1.5)MnO_(2.25). The ink was spin coated (SCS Spincoat G3P-8) onto a50×50×0 7 mm glass substrate with a 1300 rpm spin rate and 40 s spintime under an inert atmosphere (glove box) and dried at 100° C. for 3minutes leaving a molecular precursor film. The substrate was thenheated in air at 300° C. for 5 minutes to form a Li_(1.5)MnO_(2.25)cathode film with a thickness of 120 nm.

The Li/Mn ratio was found to be 1.50:1.00 by use of ICP.

Example 37 Cathode Material Prepared by Spin Coating

An ink containing 80 mol % LiMn(O^(s)Bu)₃ and 20 mol % Li₂Mn(O^(s)Bu)₄was prepared by mixing 0.450 g of solution “2” and 0.145 g of solution“4”. The final cathode material target for this ink wasLi_(1.2)MnO_(2.1). The ink was spin coated (SCS Spincoat G3P-8) onto a50×50×0 7 mm glass substrate with a 1300 rpm spin rate and 40 s spintime under an inert atmosphere (glove box) and dried at 100° C. for 3minutes leaving a molecular precursor film. The substrate was thenheated in air at 300° C. for 5 minutes to form a Li_(1.2)MnO_(2.1)cathode film with a thickness of 120 nm.

The Li/Mn ratio was found to be 1.08:1.00 by use of ICP.

Example 38 Cathode Material Prepared by Spin Coating

A cathode molecular precursor ink was prepared by dissolving 0.33 g ofLiMn(O^(s)Bu)₃ in n-butyl acetate to a concentration of 15 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.The final cathode material target for this ink was LiMnO₂.

This cathode molecular precursor ink was deposited onto a currentcollector coated substrate via spin coating (SCS Spincoat G3P-8) at 1540rpm for 40 s. 4 total layers were coated. Each layer was dried at 100°C. for 3 minutes followed by heating at 300° C. for 5 minutes in air.The final film thickness was 0.56 nm, as measured by use of a Dektakprofilometer.

The Li/Mn ratio of the cathode film was determined to be 1.05:1.00 byuse of ICP analysis.

Lithium Ion Battery Example 39 Thin Film Knife Coating and BatteryAssembly

A cathode molecular precursor ink was prepared by dissolving 0.20 g ofLiCo(O^(s)Bu)₃ in n-butyl acetate to a concentration of 10 wt %. Theresulting ink was filtered through a 0.2 μm syringe filter prior to use.The final cathode material target for this ink was LiCoO₂.

The cathode precursor ink was coated using an RK K202 knife coater witha gap of 200 μm and a speed of 15 mm/s on to a Pt and NiCr coatedborosilicate glass substrate. Each layer was dried at 100° C. for 3minutes before converting in air at 300° C. for 5 minutes. A total of 8layers were deposited resulting in a film thickness of 0.55 nm, asmeasured by use of profilometry (Dektak). The LiCoO₂ cathode film wasannealed at 580° C. for 3 minutes in dry air. The resulting annealedcathode film was then assembled into a half cell by compressing the thinfilm against a Li foil anode separated by a 0.025 mm thick film ofpolypropylene saturated with 1 mol/L LiPF₆ in 4:3:3 ethylcarbonate:dimethyl carbonate:diethyl carbonate. The open circuit voltage(OCV) of the assembled half cell was measured as 3.3V.

1. A molecular precursor compound having the empirical formula[LiMn(OR)₃] wherein each of the —OR groups is independently selectedfrom alkoxy, aryloxy, heteroaryloxy, alkenyloxy, siloxy, phosphinate,phosphonate, and phosphate.
 2. The molecular precursor compound of claim1, further comprising a number n of coordinating species L, having theempirical formula [LiM(OR)₃].n L, wherein n is from 0.01 to 8, andwherein L is selected from acetates, ethyl acetate, propyl acetates,n-propyl acetate, isopropyl acetate, butyl acetates, n-butyl acetate,sec-butyl acetate, isobutyl acetate, t-butyl acetate, isopentyl acetate,2-methylbutyl acetate, 3-methylbutyl acetate, 2,2-dimethylbutyl acetate,2,3-dimethylbutyl acetate, 2-methylpentyl acetate, 3-methylpentylacetate, 4-methylpentyl acetate, 2-methylhexyl acetate, 3-methylhexylacetate, 4-methylhexyl acetate, 5-methylhexyl acetate, 2,3-dimethylbutylacetate, 2,3-dimethylpentyl acetate, 2,4-dimethylpentyl acetate,2,2-dimethylhexyl acetate, 2,3-dimethylhexyl acetate, 2,4-dimethylhexylacetate, 2,5-dimethylhexyl acetate, 2,2-dimethylpentyl acetate,3,3-dimethylpentyl acetate, 3,3-dimethylhexyl acetate, 4,4-dimethylhexylacetate, 2-ethylpentyl acetate, 3-ethylpentyl acetate, 2-ethylhexylacetate, 3-ethylhexyl acetate, 4-ethylhexyl acetate,2-methyl-2-ethylpentyl acetate, 2-methyl-3-ethylpentyl acetate,2-methyl-4-ethylpentyl acetate, 2-methyl-2-ethylhexyl acetate,2-methyl-3-ethylhexyl acetate, 2-methyl-4-ethylhexyl acetate,2,2-diethylpentyl acetate, 3,3-diethylhexyl acetate, 2,2-diethylhexylacetate, 3,3-diethylhexyl acetate, n-heptyl acetate, n-octyl acetate,n-nonyl acetate, n-decyl acetate, n-undecyl acetate, n-dodecyl acetate,n-tridecyl acetate, n-tetradecyl acetate, n-pentadecyl acetate,n-hexadecyl acetate, n-heptadecyl acetate, n-octadecyl acetate, esters,alkylesters, arylesters, ketones, alkylketones, arylketones, acetone,alcohols, diols, thiols, methanol, ethanol, propan-1-ol, propan-2-ol,butan-1-ol, 2-methylpropan-1-ol, butan-2-ol, 2-methylpropan-2-ol,pentanol, hexanol, ethers, alkylethers, arylethers, diethylether,tetrahydrofuran, 2-methyl-tetrahydrofuran, amines, diamines, triamines,trimethylamine, ethylenediamine, acetonitrile, pyridine, and mixtures ofthe foregoing.
 3. The molecular precursor compound of claim 1, whereinthe alkoxy groups are selected from methoxy, ethoxy, n-propoxy,1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy,3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy,2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy,1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy,2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy,1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxyor 1-ethyl-2-methylpropoxy, heptyloxy, octyloxy, 2-ethylhexyloxy,nonyloxy, decyloxy, aminoalkoxy —ORNR₂ where R is alkyl, alkoxyalkoxyOROR where R is alkyl, phosphatoalkoxy —ORPR₂ where R is alkyl, andpositional isomers and combinations thereof; wherein the dialkoxy groupsare —OR²O— groups, wherein R² may be a substituted or unsubstituted,branched or unbranched alkylene chain —(CH₂)_(q)—, where q is from 1 to20; wherein the siloxy groups are selected from —OSi(OR¹)₃,—OSi(OR¹)₂R², —OSi(OR¹)R² ₂, and —OSiR² ₃, wherein R¹ and R² areindependently, for each occurrence, selected from alkyl, aryl,heteroaryl, alkenyl, silyl, and positional isomers and combinationsthereof; and wherein the phosphate groups are —OP(O)(OR¹)₂, thephosphonate groups are —OP(O)(OR¹)R², and the phosphinate groups are—OP(O)R² ₂, wherein R¹ and R² are independently, for each occurrence,selected from alkyl, aryl, heteroaryl, alkenyl, and silyl.
 4. Themolecular precursor compound of claim 1, wherein the empirical formulaof the compound is selected from [LiMn(O^(n)Bu)₃], [LiMn(O^(s)Bu)₃],[LiMn(O^(t)Bu)₃], [LiMn(O^(i)Pr)₃], [LiMn(O^(n)Pr)₃], [LiMn(OEt)₃],[LiMn(O(n-pentyl))₃], [LiMn(O(n-hexyl))₃], [LiMn(O^(t)Bu)(O^(n)Bu)₂],[LiMn(O^(s)Bu)(O^(n)Bu)₂], [LiMn(O^(i)Pr)(O^(n)Bu)₂],[LiMn(O^(n)Bu)(O^(t)Bu)₂], [LiMn(O^(n)Bu)(O^(s)Bu)₂],[LiMn(O^(n)Bu)(O^(i)Pr)₂], [LiMn(O^(s)Bu)(O^(t)Bu)₂],[LiMn(O^(n)Bu)(O^(t)Bu)₂], [LiMn(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)],[LiMn(OSi(O^(t)Bu)₃)₃], [LiMn(OSi(O^(t)Bu)₂ ^(s)Bu)₃],[LiMn(OSi(O^(t)Bu)^(s)Bu₂)₃], [LiMn(OSi^(s)Bu₃)₃],[LiMn(O^(n)Bu)(OSi(O^(t)Bu)₃)₂], [LiMn(O^(n)Bu)(OSi(O^(t)Bu)₂ ^(n)Bu)₂],[LiMn(OP(O)(O^(n)Bu)₂)₃], [LiMn(OP(O)(O^(s)Bu)₂)₃],[LiMn(OP(O)(O^(t)Bu)₂)₃], [LiMn(OP(O)(O^(i)Pr)₂)₃],[LiMn(OP(O)(O^(n)PO₂)₃], [LiMn(OP(O)(OEt)₂)₃],[LiMn(OP(O)(O(n-pentyl))₂)₃], [LiMn(OP(O)(O(n-hexyl))₂)₃],[LiMn(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₂], [LiMn(O^(s)Bu)(OP(O)(O^(n)Bu)₃)₂],[LiMn(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₂], [LiMn(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₂],[LiMn(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₂], [LiMn(O^(n)Bu)(OP(O)(O^(i)PO₂)₂],[LiMn(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₂], [LiMn(OP(O)(O^(s)Bu)₂)(O^(s)Bu)₂],and [LiMn(OP(O)(O^(i)Pr)₂)(O^(t)Bu)(O^(s)Bu)].
 5. The molecularprecursor compound of claim 1, wherein the compound has the empiricalformula selected from LiMn(O^(t)Bu)₃ and LiMn(O^(s)Bu)₃.
 6. Themolecular precursor compound of claim 1, wherein the compound has theempirical formula LiMn[OP(O)(O^(t)Bu)₂]₃.
 7. A molecular precursorcompound having the empirical formula[LiMn(OR)₄] wherein the —OR groups are independently, for eachoccurrence, selected from alkoxy, aryloxy, heteroaryloxy, alkenyloxy,siloxy, phosphinate, phosphonate, and phosphate.
 8. The molecularprecursor compound of claim 7, further comprising a number n ofcoordinating species L, having the empirical formula [LiM(OR)₄].n L,wherein n is from 0.1 to 8, and wherein L is selected from acetates,ethyl acetate, propyl acetates, n-propyl acetate, isopropyl acetate,butyl acetates, n-butyl acetate, sec-butyl acetate, isobutyl acetate,t-butyl acetate, isopentyl acetate, 2-methylbutyl acetate, 3-methylbutylacetate, 2,2-dimethylbutyl acetate, 2,3-dimethylbutyl acetate,2-methylpentyl acetate, 3-methylpentyl acetate, 4-methylpentyl acetate,2-methylhexyl acetate, 3-methylhexyl acetate, 4-methylhexyl acetate,5-methylhexyl acetate, 2,3-dimethylbutyl acetate, 2,3-dimethylpentylacetate, 2,4-dimethylpentyl acetate, 2,2-dimethylhexyl acetate,2,3-dimethylhexyl acetate, 2,4-dimethylhexyl acetate, 2,5-dimethylhexylacetate, 2,2-dimethylpentyl acetate, 3,3-dimethylpentyl acetate,3,3-dimethylhexyl acetate, 4,4-dimethylhexyl acetate, 2-ethylpentylacetate, 3-ethylpentyl acetate, 2-ethylhexyl acetate, 3-ethylhexylacetate, 4-ethylhexyl acetate, 2-methyl-2-ethylpentyl acetate,2-methyl-3-ethylpentyl acetate, 2-methyl-4-ethylpentyl acetate,2-methyl-2-ethylhexyl acetate, 2-methyl-3-ethylhexyl acetate,2-methyl-4-ethylhexyl acetate, 2,2-diethylpentyl acetate,3,3-diethylhexyl acetate, 2,2-diethylhexyl acetate, 3,3-diethylhexylacetate, n-heptyl acetate, n-octyl acetate, n-nonyl acetate, n-decylacetate, n-undecyl acetate, n-dodecyl acetate, n-tridecyl acetate,n-tetradecyl acetate, n-pentadecyl acetate, n-hexadecyl acetate,n-heptadecyl acetate, n-octadecyl acetate, esters, alkylesters,arylesters, ketones, alkylketones, arylketones, acetone, alcohols,diols, thiols, methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol,2-methylpropan-1-ol, butan-2-ol, 2-methylpropan-2-ol, pentanol, hexanol,ethers, alkylethers, arylethers, diethylether, tetrahydrofuran,2-methyl-tetrahydrofuran, amines, diamines, triamines, trimethylamine,ethylenediamine, acetonitrile, pyridine, and mixtures of the foregoing.9. The molecular precursor compound of claim 7, wherein the alkoxygroups are selected from methoxy, ethoxy, n-propoxy, 1-methylethoxy,butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, pentoxy,1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy,1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy,1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy,1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy,2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy,1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy,1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or1-ethyl-2-methylpropoxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy,decyloxy, aminoalkoxy —ORNR₂ where R is alkyl, alkoxyalkoxy OROR where Ris alkyl, phosphatoalkoxy —ORPR₂ where R is alkyl, and positionalisomers and combinations thereof; wherein the dialkoxy groups are —OR²O—groups, wherein R² may be a substituted or unsubstituted, branched orunbranched alkylene chain —(CH₂)_(q)—, where q is from 1 to 20; whereinthe siloxy groups are selected from OSi(OR¹)₃, —OSi(OR¹)₂R², OSi(OR¹)R²₂, and OSiR² ₃, wherein R¹ and R² are independently, for eachoccurrence, selected from alkyl, aryl, heteroaryl, alkenyl, silyl, andpositional isomers and combinations thereof; and wherein the phosphategroups are —OP(O)(OR¹)₂, the phosphonate groups are —OP(O)(OR¹)R², andthe phosphinate groups are —OP(O)R² ₂, wherein R¹ and R² areindependently, for each occurrence, selected from alkyl, aryl,heteroaryl, alkenyl, and silyl.
 10. The molecular precursor compound ofclaim 7, wherein the empirical formula of the compound is selected from[LiMn(O^(n)Bu)₄], [LiMn(O^(s)Bu)₄], [LiMn(O^(t)Bu)₄], [LiMn(O^(i)Pr)₄],[LiMn(O^(n)Pr)₄], [LiMn(OEt)₄], [LiMn(O(n-pentyl))₄],[LiMn(O(n-hexyl))₄], [LiMn(O^(t)Bu)(O^(n)Bu)₃],[LiMn(O^(s)Bu)(O^(n)Bu)₃], [LiMn(O^(i)Pr)(O^(n)Bu)₃],[LiMn(O^(n)Bu)(O^(t)Bu)₃], [LiMn(O^(n)Bu)(O^(s)Bu)₃],[LiMn(O^(n)Bu)(O^(i)Pr)₃], [LiMn(O^(s)Bu)(O^(t)Bu)₃],[LiMn(O^(t)Bu)(O^(s)Bu)₃], [LiMn(O^(n)Bu)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)],[LiMn(OP(O)(O^(n)Bu)₂)₄], [LiMn(OP(O)(O^(s)Bu)₂)₄],[LiMn(OP(O)(O^(t)Bu)₂)₄], [LiMn(OP(O)(O^(i)Pr)₂)₄],[LiMn(OP(O)(O^(n)Pr)₂)₄], [LiMn(OP(O)(OEt)₂)₄],[LiMn(OP(O)(O(n-pentyl))₂)₄], [LiMn(OP(O)(On-hexyl)₂)₄],[LiMn(O^(t)Bu)(OP(O)(O^(n)Bu)₂)₃], [LiMn(O^(s)Bu)(OP(O)(O^(n)Bu)₂)₃],[LiMn(O^(i)Pr)(OP(O)(O^(n)Bu)₂)₃], [LiMn(O^(n)Bu)(OP(O)(O^(t)Bu)₂)₃],[LiMn(O^(n)Bu)(OP(O)(O^(s)Bu)₂)₃], [LiMn(O^(n)Bu)(OP(O)(O^(i)PO₂)₃],[LiMn(O^(s)Bu)(OP(O)(O^(t)Bu)₂)₃], [LiMn(O^(t)Bu)(OP(O)(O^(s)Bu)₂)₃],and [LiMn(OP(O)(O^(n)Bu)₂)(O^(t)Bu)(O^(s)Bu)(O^(i)Pr)].
 11. Themolecular precursor compound of claim 7, wherein the compound has theempirical formula selected from LiMn(O^(s)Bu)₄, LiMn(O^(t)Bu)₄, andLiMn(O^(n)Bu)₄.
 12. The molecular precursor compound of claim 7, whereinthe compound has the empirical formula LiMn[OP(O)(O^(t)Bu)₂]₄.
 13. Amolecular precursor compound having the empirical formulaLi₂Mn^(x+)(OR)_(2+x), wherein x is selected from 2 and 3, and the —ORgroups are independently selected from alkoxy, aryloxy, heteroaryloxy,alkenyloxy, siloxy, phosphinate, phosphonate, and phosphate.
 14. Thecompound of claim 13, having an empirical formula selected from[Li₂Mn(OSi(O^(t)Bu)₃)(O^(s)Bu)₃], [Li₂Mn(OSi(O^(t)Bu)₃)(O^(s)Bu)₄],[Li₂Mn(O^(n)Bu)₄], [Li₂Mn(O^(s)Bu)₄], [Li₂Mn(O^(t)Bu)₄],[Li₂Mn(O(n-pentyl))₄], [Li₂Mn(O(n-hexyl))₄], [Li₂Mn(O^(t)Bu)(O^(n)Bu)₃],[Li₂Mn(O^(s)Bu)(O^(n)Bu)₃], [Li₂Mn(O^(i)Pr)(O^(n)Bu)₃],[Li₂Mn(O^(n)Bu)(O^(t)Bu)₃], [Li₂Mn(O^(n)Bu)(O^(s)Bu)₃],[Li₂Mn(O^(n)Bu)(O^(i)Pr)₃], [Li₂Mn(O^(s)Bu)(O^(t)Bu)₃],[Li₂Mn(O^(t)Bu)(O^(s)Bu)₃], [Li₂Mn(OSi(O^(n)Bu)^(n)Bu₂)₄],[Li₂Mn(OSi^(n)Bu₃)₄], [Li₂Mn(OSi(O^(s)Bu)₃)₄], [Li₂Mn(OSi(O^(s)Bu)₂^(s)Bu)₄], [Li₂Mn(OSi(O^(s)Bu)^(s)Bu₂)₄], [Li₂Mn(OSi^(s)Bu₃)₄],[Li₂Mn(OSi(O^(t)Bu)₃)₄], [Li₂Mn(OSi(O^(t)Bu)₂ ^(t)Bu)₄],[Li₂Mn(OSi^(n)Pr₃)₄], [Li₂Mn(OP(O)(O^(n)Bu)₂)₄],[Li₂Mn(OP(O)(O^(s)Bu)₂)₄], [Li₂Mn(OP(O)(O^(t)Bu)₂)₄],[Li₂Mn(OP(O)(O^(i)Pr)₂)₄], [Li₂Mn(OP(O)(O^(n)Pr)₂)₄],[Li₂Mn(OP(O)(OEt)₂)₄], [Li₂Mn(OP(O)(O^(n)Bu)^(n)Bu)₄],[Li₂Mn(OP(O)(O^(s)Bu)^(s)Bu)₄], [Li₂Mn(OP(O)(O^(t)Bu)^(t)Bu)₄],[Li₂Mn(OP(O)(O^(n)Pr)^(n)Pr)₄], [Li₂Mn(OP(O)(O^(i)Pr)^(i)Pr)₄],[Li₂Mn(OP(O)(OEt)Et)₄], [Li₂Mn(OP(O)^(n)Bu₂)₄], [Li₂Mn(OP(O)^(s)Bu₂)₄],[Li₂Mn(OP(O)^(t)Bu₂)₄], [Li₂Mn(OP(O)^(n)Pr₂)₄], [Li₂Mn(OP(O)^(i)Pr₂)₄],[Li₂Mn(OP(O)Et₂)₄], [Li₂Mn(O^(n)Bu)₅], [Li₂Mn(O^(s)Bu)₅],[Li₂Mn(O^(t)Bu)₅], [Li₂Mn(O(n-pentyl))₅], [Li₂Mn(O(n-hexyl))₅],[Li₂Mn(O^(t)Bu)₂(O^(n)Bu)₃], [Li₂Mn(O^(s)Bu)₂(O^(n)Bu)₃],[Li₂Mn(O^(i)Pr)₂(O^(n)Bu)₃], [Li₂Mn(O^(n)Bu)₂(O^(t)Bu)₃],[Li₂Mn(O^(n)Bu)₂(O^(s)Bu)₃], [Li₂Mn(O^(n)Bu)(O^(i)Pr)₄],[Li₂Mn(O^(s)Bu)(O^(t)Bu)₄], [Li₂Mn(O^(t)Bu)(O^(s)Bu)₄],[Li₂Mn(OSi(O^(n)Bu)^(n)Bu₂)₅], [Li₂Mn(OSi^(n)Bu₃)₅],[Li₂Mn(OSi(O^(s)Bu)₃)₅], [Li₂Mn(OSi(O^(s)Bu)₂ ^(s)Bu)₅],[Li₂Mn(OSi(O^(s)Bu)^(s)Bu₂)₅], [Li₂Mn(OSi^(s)Bu₃)₅],[Li₂Mn(OSi(O^(t)Bu)₃)₅], [Li₂Mn(OSi(O^(t)Bu)₂ ^(t)Bu)₅],[Li₂Mn(OSi^(n)Pr₃)₅], [Li₂Mn(OP(O)(O^(n)Bu)₂)₅],[Li₂Mn(OP(O)(O^(s)Bu)₂)₅], [Li₂Mn(OP(O)(O^(t)Bu)₂)₅],[Li₂Mn(OP(O)(O^(i)Pr)₂)₅], [Li₂Mn(OP(O)(O^(n)Pr)₂)₅],[Li₂Mn(OP(O)(OEt)₂)₅], [Li₂Mn(OP(O)(O^(n)Bu)^(n)Bu)₅],[Li₂Mn(OP(O)(O^(s)Bu)^(s)Bu)₅], [Li₂Mn(OP(O)(O^(t)Bu)^(t)Bu)₅],[Li₂Mn(OP(O)(O^(n)Pr)^(n)Pr)₅], [Li₂Mn(OP(O)(O^(i)Pr)^(i)Pr)₅],[Li₂Mn(OP(O)(OEt)Et)₅], [Li₂Mn(OP(O)^(n)Bu₂)₅], [Li₂Mn(OP(O)^(s)Bu₂)₅],[Li₂Mn(OP(O)^(t)Bu₂)₅], [Li₂Mn(OP(O)^(n)Pr₂)₅], [Li₂Mn(OP(O)^(i)Pr₂)₅],and [Li₂Mn(OP(O)Et₂)₅].
 15. A process for making a cathode material, theprocess comprising: providing one or more molecular precursor compoundsaccording to claim 1, or a mixture thereof; and heating the mixture at atemperature of from 100° C. to 800° C. to convert it to a material. 16.(canceled)
 17. (canceled)
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 19. (canceled)
 20. (canceled)21. (canceled)
 22. (canceled)
 23. (canceled)
 24. A process for making athin film cathode, the process comprising: providing a substrate coatedwith a current collector layer; providing an ink comprising one or moremolecular precursor compounds according to claim 1; and depositing theink onto the current collector layer; heating the deposited ink at atemperature of from 100° C. to 800° C. to convert it to a material. 25.The process of claim 24, wherein the heating is performed with exposureto air or oxidizing atmosphere.
 26. The process of claim 24, wherein theheating is performed under inert atmosphere after exposure to air oroxidizing atmosphere.
 27. The process of claim 24, further comprisingannealing the material at a temperature of from 400° C. to 800° C. 28.The process of claim 24, wherein the ink contains one or more dopantsource compounds having the formula M(OR)_(q), where M is selected fromMg, Y, Ti, Zr, Nb, Cr, Ru, B, Al, Bi, Sb, Sn, La, q is the same as theoxidation state of the atom M, and (OR) is independently selected fromalkoxy, aryloxy, heteroaryloxy, alkenyloxy, siloxy, phosphinate,phosphonate, and phosphate.
 29. A cathode made by the process of claim24.
 30. A lithium ion battery made with the cathode of claim
 29. 31. Aprocess for making an ink, the process comprising: providing a molecularprecursor compound according to claim 1; and dissolving the molecularprecursor compound in an acetate-solvent mixture comprising an acetateink component; wherein the acetate ink component is selected from alkylacetates, ethyl acetate, propyl acetates, butyl acetates, n-butylacetate, sec-butyl acetate, tert-butyl acetate, hexyl acetates, arylacetates, alkenyl acetates, and heteroaryl acetates; and wherein thesolvent is selected from alcohol, methanol, ethanol, isopropyl alcohol,sec-butanol, thiols, butanol, butanediol, glycerols, alkoxyalcohols,glycols, 1-methoxy-2-propanol, acetone, ethylene glycol, propyleneglycol, propylene glycol laurate, ethylene glycol ethers, diethyleneglycol, triethylene glycol monobutylether, propylene glycolmonomethylether, 1,2-hexanediol, ethers, diethyl ether, aliphatichydrocarbons, aromatic hydrocarbons, dodecane, hexadecane, pentane,hexane, heptane, octane, isooctane, decane, cyclohexane, p-xylene,m-xylene, o-xylene, benzene, toluene, xylene, tetrahydrofuran,2-methyltetrahydrofuran, siloxanes, cyclosiloxanes, silicone fluids,halogenated hydrocarbons, dibromomethane, dichloromethane,dichloroethane, trichloroethane chloroform, methylene chloride,acetonitrile, esters, acrylates, isobornyl acrylate, 1,6-hexanedioldiacrylate, polyethylene glycol diacrylate, ketones, methyl ethylketone, cyclohexanone, butyl carbitol, cyclopentanone, lactams,N-methylpyrrolidone, N-(2-hydroxyethyl)-pyrrolidone, cyclic acetals,cyclic ketals, aldehydes, amines, diamines, amides, dimethylformamide,methyl lactate, oils, natural oils, terpenes, and mixtures thereof. 32.(canceled)
 33. (canceled)
 34. (canceled)
 35. A cathode material havingthe formula Li_((1+x))MnO_((2+x/2)), where x is from 0.01 to
 1. 36.(canceled)
 37. (canceled)
 38. (canceled)
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 40. (canceled)